Strategies to improve the electrochemical performance of electrodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yang, Ming-Che

Lithium-ion batteries are widely used in consumer market because of their lightweight and rechargeable property. However, for the application as power sources of hybrid electric vehicles (HEVs), which need excellent cycling performance, high energy density, high power density, capacity, and low cost, new materials still need to be developed to meet the demands. In this dissertation work, three different strategies were developed to improve the properties of the electrode of lithium batteries. First, the voltage profile and lithium diffusion battier of LiM1/2Mn 3/2O4 (M=Ti, V, Cr, Fe, Co, Ni and Cu) were predicted by first principles theory. The computation results suggest that doping with Co or Cu can potentially lower Li diffusion barrier compared with Ni doping. Our experimental research has focused on LiNixCuyMn 2-x-yO4 (0

Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life

DOE PAGES

Li, Yue Ru; Poyraz, Altug S.; Hu, Xiaobing; ...

2017-01-01

Birnessite type layered manganese dioxides (δ-MnO 2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li +, Na +, and Mg 2+ batteries due to fast ion diffusion through their negatively charged δ-MnO 2 sheets separated by interlayer cations and a stable Mn 3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu 0 0.03Cu 2+ 0.21Na 0.12MnO 2·0.9H 2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM).more » The mixed valent nature of intercalated Cu 0 and Cu 2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu 2+ only intercalated (Cu 0.26MnO 2·1.0H 2O) and Cu free Na birnessite (Na 0.40MnO 2·1.0H 2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu 0 modified samples was much lower than that of Cu 2+ and Cu free birnessite, indicating that the presence of a small amount of Cu 0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.« less

Structural and electrochemical study of positive electrode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Jiang, Meng

The research presented in this dissertation focuses on a combined study of the electrochemistry and the structure of positive electrode materials for Li ion batteries. Li ion batteries are one of the most advanced energy storage systems and have been the subject of numerous scientific studies in recent decades. They have been widely used for various mobile devices such as cell phones, laptop computers and power tools. They are also promising candidates as power sources for automotive applications. Although intensive research has been done to improve the performance of Li ion batteries, there are still many remaining challenges to overcome so that they can be used in a wider range of applications. In particular, cheaper and safer electrodes are required with much higher reversible capacity. The series of layered nickel manganese oxides [NixLi 1/3-2x/3Mn2/3- x/3]O2 (0 < x < 1/2) are promising alternatives for Li2CoO2, the commercial positive electrode materials in Li ion batteries, because of their lower cost and higher safety and abuse tolerance, when lithium is removed from their structure. Compounds with x<1/2, in which the total Li content is higher than transition metal content, are referred as "Li-excess" materials. The "Li2MnO3-like" region is always present in this type of materials, and the overcapacity is obtained in the first charge process, which is not reversible in the following cycles. A combined X-ray diffraction, solid state nuclear magnetic resonance and X-ray absorption spectroscopy study is performed to investigate the effect of synthetic methods on the structure, to probe the structural change of the materials during cycling and to understand the electrochemical reaction mechanism. The conversion compounds are also investigated because of their high capacities. Since the various compounds have different voltage windows, they can have potential applications as both cathodes and anodes. Solid state nuclear magnetic resonance is used to study the change in the local environment of the structure during the cycling process. Two systems are included in this work, including iron fluorides and Cu-containing materials. A comparison study has been performed on FeF3 and FeF2. Different discharge reaction mechanisms are clarified for each compound, and possible phase transitions are proposed as well. As for the Cu-containing systems, three compounds were chosen with different anions: CuS, CuO and CuF2. The reaction mechanisms are studied by 63Cu, 7Li and 19F NMR and supported by powder X-ray diffraction.

A New CuO-Fe2 O3 -Mesocarbon Microbeads Conversion Anode in a High-Performance Lithium-Ion Battery with a Li1.35 Ni0.48 Fe0.1 Mn1.72 O4 Spinel Cathode.

PubMed

Di Lecce, Daniele; Verrelli, Roberta; Campanella, Daniele; Marangon, Vittorio; Hassoun, Jusef

2017-04-10

A ternary CuO-Fe 2 O 3 -mesocarbon microbeads (MCMB) conversion anode was characterized and combined with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 spinel cathode in a lithium-ion battery of relevant performance in terms of cycling stability and rate capability. The CuO-Fe 2 O 3 -MCMB composite was prepared by using high-energy milling, a low-cost pathway that leads to a crystalline structure and homogeneous submicrometrical morphology as revealed by XRD and electron microscopy. The anode reversibly exchanges lithium ions through the conversion reactions of CuO and Fe 2 O 3 and by insertion into the MCMB carbon. Electrochemical tests, including impedance spectroscopy, revealed a conductive electrode/electrolyte interface that enabled the anode to achieve a reversible capacity value higher than 500 mAh g -1 when cycled at a current of 120 mA g -1 . The remarkable stability of the CuO-Fe 2 O 3 -MCMB electrode and the suitable characteristics in terms of delivered capacity and voltage-profile retention allowed its use in an efficient full lithium-ion cell with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 cathode. The cell had a working voltage of 3.6 V and delivered a capacity of 110 mAh g cathode -1 with a Coulombic efficiency above 99 % after 100 cycles at 148 mA g cathode -1 . This relevant performances, rarely achieved by lithium-ion systems that use the conversion reaction, are the result of an excellent cell balance in terms of negative-to-positive ratio, favored by the anode composition and electrochemical features. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of digestion methods for total elemental analysis of peat and separation of its organic and inorganic components

USGS Publications Warehouse

Papp, C.S.E.; Harms, T.F.

1985-01-01

In order to find the most efficient digestion method for the total elemental recovery in peat, ten samples were subjected to different techniques and analysed for Ca, Mg, Fe, AI, Na, K, Mn, P, Zn, Cu, Li, Cd, Co, Ni, Pb and Si using atomic-absorption spectrophotometry. The most satisfactory procedures were dry ashing followed by hydrofluoric acid treatment and wet digestion using a mixture of hot nitric, perchloric and hydrofluoric acids. The wet digestion offers the advantage of a single decomposition method for the determination of Ca, Mg, Fe, AI, K, Na, Mn, Cu, Li, Zn and P. An alkaline fusion technique was required for the determination of Si. Hydrogen peroxide was used to separate the peat into its organic and inorganic components, leading to the total recovery of the elements for both fractions.

Anode materials for lithium ion batteries

DOEpatents

Abouimrane, Ali; Amine, Khalil

2017-04-11

An electrochemical device includes a composite material of general Formula (1-x)J-(x)Q wherein: J is a metal carbon alloy of formula Sn.sub.zSi.sub.z'Met.sub.wMet'.sub.w'C.sub.t; Q is a metal oxide of formula A.sub..gamma.M.sub..alpha.M'.sub..alpha.'O.sub..beta.; and wherein: A is Li, Na, or K; M and M' are individually Ge, Mo, Al, Ga, As, Sb, Te, Ti, Ta, Zr, Ca, Mg, Sr, Ba, Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Rt, Ru or Cd; Met and Met' are individually Ge, Mo, Al, Ga, As, Sb, Te, Ti, Ta, Zr, Ca, Mg, Sr, Ba, Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Rt, Ru or Cd; 0

Origin discrimination of defatted pork via trace elements profiling, stable isotope ratios analysis, and multivariate statistical techniques.

PubMed

Park, Yu Min; Lee, Cheong Mi; Hong, Joon Ho; Jamila, Nargis; Khan, Naeem; Jung, Jong-Hyun; Jung, Young-Chul; Kim, Kyong Su

2018-09-01

This study verified the origin of 346 defatted Korean and non-Korean pork samples via trace elements profiling, and C and N stable isotope ratios analysis. The analyzed elements were 6 Li, 7 Li, 10 B, 11 B, 51 V , 50 Cr, 52 Cr, 53 Cr, 55 Mn, 58 Ni, 60 Ni, 59 Co, 63 Cu, 65 Cu, 64 Zn, 66 Zn, 69 Ga, 71 Ga, 75 As, 82 Se, 84 Sr, 86 Sr, 87 Sr, 88 Sr, 85 Rb, 94 Mo, 95 Mo, 97 Mo, 107 Ag, 109 Ag, 110 Cd, 111 Cd, 113 Cd, 112 Cd, 114 Cd, 116 Cd, 133 Cs, 206 Pb, 207 Pb, and 208 Pb. Content (mg/kg) of 51 V (0.012), 50 Cr (0.882), 75 As (0.017), 85 Rb (57.7), and 87 Sr (46.3) were high in Korean pork samples whereas 6 Li, 7 Li, 59 Co, 55 Mn, 58 Ni, 84 Sr, 86 Sr, 88 Sr, 111 Cd, and 133 Cs were found higher in non-Korean samples. The results of discriminant analysis showed that the trace elements content and stable isotope ratios were significant for the discrimination of geographical origins with a perfect discrimination rate of 100%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chemical, structural, and electrochemical characterization of 5 V spinel and complex layered oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Tiruvannamalai Annamalai, Arun Kumar

2007-12-01

Lithium ion batteries have revolutionized the portable electronics market since their commercialization first by Sony Corporation in 1990. They are also being intensively pursued for electric and hybrid electric vehicle applications. Commercial lithium ion cells are currently made largely with the layered LiCoO 2 cathode. However, only 50% of the theoretical capacity of LiCoO 2 can be utilized in practical cells due to the chemical and structural instabilities at deep charge as well as safety concerns. These drawbacks together with the high cost and toxicity of Co have created enormous interest in alternative cathodes. In this regard, spinel LiMn2O4 has been investigated widely as Mn is inexpensive and environmentally benign. However, LiMn 2O4 exhibits severe capacity fade on cycling, particularly at elevated temperatures. With an aim to overcome the capacity fading problems, several cationic substitutions to give LiMn2-yMyO 4 (M = Cr, Fe, Co, Ni, and Cu) have been pursued in the literature. Among the cation-substituted systems, LiMn1.5Ni0.5O 4 has become attractive as it shows a high capacity of ˜ 130 mAh/g (theoretical capacity: 147 mAh/g) at around 4.7 V. With an aim to improve the electrochemical performance of the 5 V LiMn 1.5Ni0.5O4 spinel oxide, various cation-substituted LiMn1.5-yNi0.5-zMy+zO4 (M = Li, Mg, Fe, Co, and Zn) spinel oxides have been investigated by chemical lithium extraction. The cation-substituted LiMn1.5-yNi0.5-zM y+zO4 spinel oxides exhibit better cyclability and rate capability in the 5 V region compared to the unsubstituted LiMn1.5Ni 0.5O4 cathodes although the degree of manganese dissolution does not vary significantly. The better electrochemical properties of LiMn 1.5-yNi0.5-zMy+zO4 are found to be due to a smaller lattice parameter difference among the three cubic phases formed during the charge-discharge process. In addition, while the spinel Li1-xMn1.58Ni0.42O4 was chemically stable, the spinel Li1-xCo2O4 was found to exhibit both proton insertion and oxygen loss at deep lithium extraction due to the chemical instability arising from a overlap of the Co3+/4+:3d band on the top of the O2-:2p band. The irreversible oxygen loss during the first charge and the consequent reversible capacities of the solid solutions between Li[Li1/3Mn 2/3]O2 and Li[Co1-yNiy]O2 has been found to be determined by the amount of lithium in the transition metal layer of the O3 type layered structure. The lithium content in the transition metal layer is, however, sensitively influenced by the tendency of Ni 3+ to get reduced to Ni2+ and the consequent volatilization of lithium during synthesis. Moreover, high Mn4+ content causes a decrease in oxygen mobility and loss. In addition, the chemically delithiated samples were found to adopt either the parent O3 type structure or the new P3 or O1 type structures depending upon the composition and synthesis temperature of the parent samples and the proton content inserted into the delithiated sample. In essence, the chemical and structural stabilities and the electrochemical performance factors of the layered (1-z) Li[Li1/3 Mn2/3]O2 · (z) Li[Co1-yNi y]O2 solid solution cathodes are found to be maximized by optimizing the contents of the various ions.

Evaluated the Twenty-Six Elements in the Pectoral Muscle of As-Treated Chicken by Inductively Coupled Plasma Mass Spectrometry.

PubMed

Sun, Bonan; Xing, Mingwei

2016-02-01

This study assessed the impacts of dietary arsenic trioxide on the contents of 26 elements in the pectoral muscle of chicken. A total of 100 Hy-line laying cocks were randomly divided into two groups (n = 50), including an As-treated group (basic diet supplemented with arsenic trioxide at 30 mg/kg) and a control group (basal diet). The feeding experiment lasted for 90 days and the experimental animals were given free access to feed and drinking water. The elements lithium (Li), boron (B), natrum (Na), magnesium (Mg), aluminium (AI), silicium (Si), kalium (K), calcium (Ca), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co.), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), stannum (Sn), stibium (Sb), barium (Ba), hydrargyrum (Hg), thallium (Tl) and plumbum (Pb) in the pectoral muscles were determined using inductively coupled plasma mass spectrometry (ICP-MS). The resulted data indicated that Li, Na, AI, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ba, Tl and Pb were significantly increased (P < 0.05) in chicken exposed to As2O3 compared to control chicken, while Mg, Si, K, As and Cd decreased significantly (P < 0.05). These results suggest that ICP-MS determination of elements in chicken tissues enables a rapid analysis with good precision and accuracy. Supplementation of high levels of As affected levels of 20 elements (Li, Na, AI, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ba, Tl, Pb, Mg, Si, K, As and Cd) in the pectoral muscles of chicken. Thus, it is needful to monitor the concentration of toxic metal (As) in chicken for human health.

Deficiency of macro- and micronutrients induced by Lentinula edodes.

PubMed

Grotto, D; Gerenutti, M; Souza, V C O; Barbosa, F

2015-01-01

Mushroom Lentinula edodes has been widely studied therapeutically. However, there is no data regarding its daily intake level safety. Since L. edodes has many active compounds known to bind to metals, we evaluated macro and micronutrients in liver and kidney of healthy rats after subchronic exposure to L. edodes . Rats were divided into four groups, receiving water and L. edodes at 100, 400 and 800 mg/kg/day. The treatment lasted 30 days. Essential elements (Zn, Cu, Mg, Fe, Mn, Se, Co, Mo, and Li) were analyzed in an inductively coupled plasma mass spectrometer. Our results demonstrated a significant decrease in Cu, Fe, Mn and Co levels in liver of rats receiving L. edodes at the highest doses. In kidney, Mn, Mo and Li concentrations significantly dropped in the groups exposed to the highest doses. In this way, an important point is revealed concerning the food safety from L. edodes , once its chronic and high consumption could contribute to macro and micronutrients deficiency. Additionally, we speculate that the daily use of L. edodes could be unsuccessful for patients in mineral therapy besides being able to be unsafe for individuals with some propensity to mineral deficiency.

The occurrence and distribution of trace metals in the Mississippi River and its tributaries

USGS Publications Warehouse

Taylor, Howard E.; Garbarino, J.R.; Brinton, T.I.

1990-01-01

Quantitative and semiquantitative analyses of dissolved trace metals are reported for designated sampling sites on the Mississippi River and its main tributaries utilizing depth-integrated and width-integrated sampling technology to collect statistically representative samples. Data are reported for three sampling periods, including: July-August 1987, November-December 1987, and May-June 1988. Concentrations of Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Pb, Sr, Tl, U, V, and Zn are reported quantitatively, with the remainder of the stable metals in the periodic table reported semiquantitatively. Correlations between As and V, Ba and U, Cu and Zn, Li and Ba, and Li and U are significant at the 99% confidence level for each of the sampling trips. Comparison of the results of this study for selected metals with other published data show generally good agreement for Cr, Cu, Fe, and Zn, moderate agreement for Mo, and poor agreement for Cd and V.

Design and Properties Prediction of AMCO3F by First-Principles Calculations.

PubMed

Tian, Meng; Gao, Yurui; Ouyang, Chuying; Wang, Zhaoxiang; Chen, Liquan

2017-04-19

Computer simulation accelerates the rate of identification and application of new materials. To search for new materials to meet the increasing demands of secondary batteries with higher energy density, the properties of some transition-metal fluorocarbonates ([CO 3 F] 3- ) were simulated in this work as cathode materials for Li- and Na-ion batteries based on first-principles calculations. These materials were designed by substituting the K + ions in KCuCO 3 F with Li + or Na + ions and the Cu 2+ ions with transition-metal ions such as Fe 2+ , Co 2+ , Ni 2+ , and Mn 2+ ions, respectively. The phase stability, electronic conductivity, ionic diffusion, and electrochemical potential of these materials were calculated by first-principles calculations. After taking comprehensive consideration of the kinetic and thermodynamic properties, LiCoCO 3 F and LiFeCO 3 F are believed to be promising novel cathode materials in all of the calculated AMCO 3 F (A = Li and Na; M = Fe, Mn, Co, and Ni). These results will help the design and discovery of new materials for secondary batteries.

HUMAN SCALP HAIR: AN ENVIRONMENTAL EXPOSURE INDEX FOR TRACE ELEMENTS. II. SEVENTEEN TRACE ELEMENTS IN FOUR NEW JERSEY COMMUNITIES (1972)

EPA Science Inventory

Seventeen trace elements - arsenic (As), barium (Ba), boron (B), cadmium (Cd), chromium (Cr), copper (Cu), Iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), nickle (Ni), selenium (Se), silver (Ag), tin (Sn), vanadium (V), and zinc (Zn) - were measured in human sca...

The use of olive tree (Olea europaea L.) leaves as a bioindicator for environmental pollution in the Province of Aydın, Turkey.

PubMed

Turan, Dilek; Kocahakimoglu, Cemre; Kavcar, Pınar; Gaygısız, Handan; Atatanir, Levent; Turgut, Cafer; Sofuoglu, Sait C

2011-03-01

In this study, olive tree leaves, collected from 50 sampling sites throughout the Province of Aydın, Turkey, were used to estimate level of pollution by measuring Al, As, B, Ba, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, and Zn concentrations and calculating pollution factor (PF) values. After sample preparation, collected leaves were microwave digested, and extracts were analyzed by an inductively coupled plasma-mass spectrometer. The maximum PF values were ≥10 for a number of elements ranging from 11-13 (Al, As, Cr, Fe, Mn, Ni) to >100 for Cu, Li, and Na. Urban-rural and roadside-nonroadside concentration comparisons showed that some of the elements (As, Cu, and Pb) were at significantly higher levels on urban and/or roadside sampling sites. Correlations and factor analysis showed that there may be common sources for some elements, which included several soil types and anthropogenic activities. Based on the results of the statistical source apportionment, possible sources were narrowed down with help of the constructed elemental concentration maps. In conclusion, utilization of olive tree leaves for biomonitoring and assessment of environmental pollution was shown to be possible in the Mediterranean region where they are indigenous and cultivated.

Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger

NASA Astrophysics Data System (ADS)

Horeh, N. Bahaloo; Mousavi, S. M.; Shojaosadati, S. A.

2016-07-01

In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.

Age-related differences in hair trace elements: a cross-sectional study in Orenburg, Russia.

PubMed

Skalnaya, Margarita G; Tinkov, Alexey A; Demidov, Vasily A; Serebryansky, Eugeny P; Nikonorov, Alexandr A; Skalny, Anatoly V

2016-09-01

Age-related differences in the trace element content of hair have been reported. However, some discrepancies in the data exist. The primary objective of this study was to estimate the change in hair trace elements content in relation to age. Six hundred and eighteen women and 438 men aged from 10-59 years took part in the current cross-sectional study. Hair Cr, Mn, Ni, Si, Al, As, Be, Cd and Pb tended to decrease with age in the female sample, whereas hair Cu, Fe, I, Se, Li and Sn were characterised by an age-associated increase. Hair levels of Cr, Cu, I, Mn, Ni, Si and Al in men decreased with age, whereas hair Co, Fe, Se, Cd, Li and Pb content tended to increase. Hair mercury increased in association with age in men and in women, whereas hair vanadium was characterised by a significant decrease in both sexes. The difference in hair trace element content between men and women decreased with age. These data suggest that age-related differences in trace element status may have a direct implication in the ageing process.

Corrosion and Potentiostatic Polarization of an Al-Cu-Li Alloy under Tensile Stress

NASA Astrophysics Data System (ADS)

Li, Jin-feng; Zheng, Zi-qiao

The stress corrosion cracking (SCC) of an Al-3.8Cu-1.5Li-0.5Zn-0.5Mg-0.3Mn alloy in 3.5% NaCl solution was studied through using slow strain rate tension(SSRT). The potentiodynamic polarization and anodic potentiostastic polarization of the stressed and stress free alloy with T6 temper were investigated. The tensile stress decreased the break down potential. The alloy was sensitive to intergranular SCC (IGSCC), due to the continuous distribution of anodic phase of T2(Al6CuLi3) along the grain boundary. During the potentiostastic polarization, the current-time curve of the stressed alloy displayed a repeated transient feature that the current increased suddenly followed by a slower recovery, and corrosion crack appeared along the grain boundary. While the stress free alloy did not show this current feature and corrosion crack along the grain boundary. The repeated current transient was associated with the crack tip propagation and crack wall passivation. This feature may be used to analyze the SCC process.

Valency and spin states of substituent cations in Bi2.15Sr1.85CaCu2O8+δ

NASA Astrophysics Data System (ADS)

Benseman, T. M.; Cooper, J. R.; Zentile, C. L.; Lemberger, L.; Balakrishnan, G.

2011-10-01

We studied the valency and spin behavior of M = Mn, Fe, Co, Li, and Al in the high-temperature superconducting compound Bi2.15Sr1.85Ca(Cu1-zMz)2O8+δ (Bi-2212) for small values of z. Mn, Fe, and Co retain their magnetic moments, and our thermopower and magnetic susceptibility data imply ionization states Mn3+, Fe2+, and Co2+, while Li and Al are accommodated in the charge reservoir layers. Single-crystal studies show that the susceptibility of Co2+ ions in Bi-2212 is strongly anisotropic, with a weak anisotropy detected for Mn3+ and none for Fe2+. Fits to a pseudogap formula for a pure Bi-2212 crystal suggest that the spin susceptibility of the host compound is more anisotropic than previously realized. Data in the superconducting state allow us to compare the pair-breaking properties of the different impurities. Several aspects of the data, including the stronger suppression of the superconducting transition temperature Tc by Co compared with Fe for underdoped and optimally doped samples, show that the d-level structure of the magnetic ions and multiorbital effects are important. We also find that the temperatures of the magnetization crossing points are equal to the low-field Tc values to within 1% or 2%. This agrees with a 2D thermodynamic fluctuation argument given by Junod

A Monte Carlo study of the quality dependence factors of common TLD materials in photon and electron beams.

PubMed

Mobit, P N; Nahum, A E; Mayles, P

1998-08-01

A Monte Carlo simulation of the quality dependence of different TL materials, in the form of discs 3.61 mm in diameter and 0.9 mm thick, in radiotherapy photon beams relative to 60Co gamma-rays has been performed. The beam qualities ranged from 50 kV to 25 MV x-rays. The TL materials were: CaF2, CaSO4, LiF and Li2B4O7. The effects of the dopants on energy deposition in the TL material have also been determined for the highly sensitive LiF:Mg:Cu:P (TLD-100H) and for CaF2:Mn. It was found that there was a significant difference in the quality dependence factor derived from Monte Carlo simulations between LiF and LiF:Mg:Cu:P but not between CaF2 and CaF2:Mn. The quality dependence factors for Li2B4O7 varied from 0.990 +/- 0.008 (1 sd) for 25 MV x-rays to 0.940 +/- 0.009 (1 sd) for 50 kV x-rays relative to 60Co gamma-rays; Monte Carlo simulations were also performed for Li2B4O7 in megavoltage electron beams. For CaF2, the quality dependence factor varied from 0.927 +/- 0.008 (1 sd) for 25 MV x-rays to 10.561 +/- 0.008 (1 sd) for 50 kV x-rays. The figure for CaSO4 ranged from 0.943 +/- 0.008 (1 sd) for 25 MV x-rays to 9.010 +/- 0.008 (1 sd) for 50 kV x-rays. The quality dependence factor for CaF2 increases by up to 5% with depth and by up to 15% with field size for the kilovoltage x-ray beams. For LiF-TLD, however, there was no significant dependence on the field size or depth of irradiation in the kilovoltage energy range.

Transition-Metal Mixing and Redox Potentials in Li x (M 1–y M' y )PO 4 (M, M' = Mn, Fe, Ni) Olivine Materials from First-Principles Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snydacker, David H.; Wolverton, Chris

The performance of olivine cathode materials can be improved using core/shell structures such as LiMnPO 4/LiFePO 4 and LiMnPO 4/LiNiPO 4. We use density functional theory to calculate the energetics, phase stability, and voltages of transition-metal mixing for a series of olivine phosphate materials. For LiMn 1–yFe yPO 4, LiFe 1–yNi yPO 4, and LiMn 1–yNi yPO 4, we find phase-separating tendencies with (mean-field) maximum miscibility gap temperatures of 120, 320, and 760 K respectively. At room temperature, we find that Mn is completely miscible in LiFePO 4, whereas Mn solubility in LiNiPO 4 is just 0.3%. Therefore, we suggestmore » that core/shell LiMnPO 4/LiNiPO 4 particles could be more effective at containing Mn in the particle core and limiting Mn dissolution into the electrolyte relative to LiMnPO 4/LiFePO 4 particles. We calculate shifts in redox potentials for dilute transition metals, M, substituted into Li xM'PO 4 host materials. Unmixed Li xMnPO 4 exhibits a redox potential of 4.0 V, but we find that dilute Mn in a LiNiPO 4 shell exhibits a redox potential of 4.3 V and therefore remains redox inactive at lower cathode potentials. We find that strain plays a large role in the redox potentials of some mixed systems (Li xMn 1–yFe yPO 4) but not others (Li xMn 1–yNi yPO 4).« less

Synthesis, characterization and electrochemical performance of Al-substituted Li₂MnO₃

DOE PAGES

Dhital, Chetan; Huq, Ashfia; Paranthaman, Mariappan Parans; ...

2015-08-08

Li 2MnO 3 is known to be electrochemically inactive due to Mn in tetravalent oxidation state. Several compositions such as Li 2MnO 3 , Li 1.5Al 0.17MnO 3, Li 1.0Al 0.33MnO 3 and Li 0.5Al 0.5MnO 3 were synthesized by a sol–gel Pechini method. All the samples were characterized with x-ray diffraction, Raman, x-ray photoelectron spectroscopy, scanning electron microscopy, Tap density and BET analyzer. X-ray diffraction patterns indicated the presence of monoclinic phase for pristine Li 2MnO 3and mixed monoclinic/spinel phases (Li 2 - xMn 1 - yAl x + yO 3 + z) for Al-substituted Li 2MnO 3compounds. Themore » Al substitution seems to occur both at Li and Mn sites, which could explain the presence of spinel phase. X-ray photoelectron spectroscopy for Mn 2p orbital reveals a significant decrease in binding energy for Li 1.0Al 0.33MnO 3 and Li 0.5Al 0.5MnO 3 compounds. Cyclic voltammetry, charge/discharge cycles and electrochemical impedance spectroscopy were also performed. A discharge capacity of 24 mAh g -1 for Li 2MnO 3, 68 mAh g -1 for Li 1.5Al 0.17MnO 3, 58 mAh g -1 for Li 1.0Al 0.33MnO 3 and 74 mAh g -1 for Li 0.5Al 0.5MnO 3 were obtained. As a result, aluminum substitutions increased the formation of spinel phase which is responsible for cycling.« less

Mechanisms responsible for two possible electrochemical reactions in Li1.2Ni0.13Mn0.54Co0.13O2 used for lithium ion batteries

NASA Astrophysics Data System (ADS)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei; Tamura, Kazuhisa

2018-02-01

Two electrochemical reactions are possible in regard to Li1.2Ni0.13Mn0.54Co0.13O2 (0.5Li2MnO3-0.5LiNi0.33Mn0.33Co0.33O2), viz, Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like reactions. The open circuit potential (OCP) and changes in crystal structure during the charge-discharge process of Li1.2Ni0.13Mn0.54Co0.13O2 were investigated to clarify the mechanism responsible for the two reactions. Li2MnO3 and LiNi0.33Mn0.33Co0.33O2 were separately prepared for the investigation, and the OCPs and crystal structures in these cathodes were measured and then compared with those for Li1.2Ni0.13Mn0.54Co0.13O2. The results obtained using X-ray diffraction (XRD) indicated that two phases existed in Li1.2Ni0.13Mn0.54Co0.13O2. The changes in crystal structure of the two phases during the charge-discharge process were similar to those in Li2MnO3 and LiNi0.33Mn0.33Co0.33O2. This indicated that two phases, viz, Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like, existed in Li1.2Ni0.13Mn0.54Co0.13O2. Li2MnO3-like, LiNi0.33Mn0.33Co0.33O2-like, and Li2MnO3-like phases were found to contribute mainly to electrochemical reactions in the low, middle, and high state of charge (SOC) ranges during the charge process from the results obtained using XRD and electrochemical measurements carried out on Li1.2Ni0.13Mn0.54Co0.13O2. In contrast, the Li2MnO3-like and LiNi0.33Mn0.33Co0.33O2-like phases mainly contributed to electrochemical reactions in the low and high SOC ranges during the discharge process. Furthermore, the high polarization and potential decay during the charge-discharge cycling of Li1.2Ni0.13Mn0.54Co0.13O2 were mainly attributed to the Li2MnO3-like phase.

HUMAN SCALP HAIR: AN ENVIRONMENTAL EXPOSURE INDEX FOR TRACE ELEMENTS. III. SEVENTEEN TRACE ELEMENTS IN BIRMINGHAM, ALABAMA AND CHARLOTTE, NORTH CAROLINA (1972)

EPA Science Inventory

Seventeen trace elements - arsenic (As), barium (Ba), boron, (B), cadmium, (Cd), chromium (Cr), copper (Cu), Iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), nickel (Ni), selenium (Se), silver (Ag), tin (Sn), vanadium (V), and Zinc (Zn) - were measured in human s...

Redox potential trend with transition metal elements in lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Chen, Zhenlian; Li, Jun

2013-03-01

First-principles calculations are performed to investigate the relationship between the intrinsic voltage and element-lattice for the popular transition metal oxides and polyoxyanionic compounds as cathode materials for lithium-ion batteries. A V-shape redox potential in olivine phosphates LiMPO4 and orthogonal silicates Li2MSiO4 (M =Mn, Fe, Co, Ni), and an N-shape one in layered oxides LiMO2 (M =Mn, Fe, Co, Ni, Cu) relative to transition metal M elements are found to be inversely characteristic of electronic energy contribution, which costs energy in the lithiation process and is defined as electron affinity. The maxima of electron affinity, locating at different elements for different types of crystal lattices are determined by delectronic configurations that cross the turning point of a full occupancy of electronic bands, which is determined by the cooperative effect of crystal field splitting and intraionic exchange interactions. The Ningbo Key Innovation Team, National Natural Science Foundation of China, Postdoctoral Foundation of China

Electrochemical performances of LiMnPO4 synthesized from non-stoichiometric Li/Mn ratio.

PubMed

Xiao, Jie; Chernova, Natasha A; Upreti, Shailesh; Chen, Xilin; Li, Zheng; Deng, Zhiqun; Choi, Daiwon; Xu, Wu; Nie, Zimin; Graff, Gordon L; Liu, Jun; Whittingham, M Stanley; Zhang, Ji-Guang

2011-10-28

In this paper, the influences of the lithium content in the starting materials on the final performances of as-prepared Li(x)MnPO(4) (x hereafter represents the starting Li content in the synthesis step which does not necessarily mean that Li(x)MnPO(4) is a single phase solid solution in this work.) are systematically investigated. It has been revealed that Mn(2)P(2)O(7) is the main impurity when Li < 1.0 while Li(3)PO(4) begins to form once x > 1.0. The interactions between Mn(2)P(2)O(7) or Li(3)PO(4) impurities and LiMnPO(4) are studied in terms of the structural, electrochemical, and magnetic properties. At a slow rate of C/50, the reversible capacity of both Li(0.5)MnPO(4) and Li(0.8)MnPO(4) increases with cycling. This indicates a gradual activation of more sites to accommodate a reversible diffusion of Li(+) ions that may be related to the interaction between Mn(2)P(2)O(7) and LiMnPO(4) nanoparticles. Among all of the different compositions, Li(1.1)MnPO(4) exhibits the most stable cycling ability probably because of the existence of a trace amount of Li(3)PO(4) impurity that functions as a solid-state electrolyte on the surface. The magnetic properties and X-ray absorption spectroscopy (XAS) of the MnPO(4)·H(2)O precursor, pure and carbon-coated Li(x)MnPO(4) are also investigated to identify the key steps involved in preparing a high-performance LiMnPO(4). This journal is © the Owner Societies 2011

Enhanced electrochemical performance of LiMn2O4 by constructing a stable Mn2+-rich interface

NASA Astrophysics Data System (ADS)

Lu, Zhongpei; Lu, Xiaojun; Ding, Jingjing; Zhou, Ting; Ge, Tao; Yang, Gang; Yin, Fan; Wu, Mingfang

2017-12-01

Spinel LiMn2O4 has drawn continuous attentions due to its low cost, good electrochemical performance, environmental friendliness and natural abundant resources. In view of its severe capacity fading, some types of manganese-based compounds with different Mn oxidation states are selected to protect bare LiMn2O4 by constructing a stable coating layer. In this work, LiMn2O4@LiMnPO4 composite, spherical LiMn2O4 (LMO) as core and Mn2+-rich phase of LiMnPO4 (LMP) as shell, is designed and synthesized. Two composites of LiMn2O4 particles coated with 3 wt% and 10 wt% LiMnPO4 have been compared studied. After 100 cycles at 0.5C rate, the two samples deliver capacity retentions of 96.63% and 93.23% of their initial capacities. Moreover, LMO coated by 3 wt% LiMnPO4 delivers 100.3 mAh g-1 after 200 cycles at 10C rate and 76.3 mAh g-1 after 1000 cycles at 20C rate, much higher than bare LiMn2O4 with 90 mAh g-1 and 45.8 mAh g-1, respectively. This core-shell structure with Mn2+-rich phase as a coating layer effectively enhance the material's cycling performance and rate capacity by reducing the contact of LiMn2O4 with electrolyte.

Spatial and temporal characterization of trace elements and nutrients in the Rawal Lake Reservoir, Pakistan using multivariate analysis techniques.

PubMed

Malik, Riffat Naseem; Nadeem, Muhammad

2011-12-01

Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO (4) (3-) , NO(3)-N, and SO (4) (2-) ) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl(-), and NH(4)-N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.

Estimation of dietary intake and target hazard quotients for metals by consumption of wines from the Canary Islands.

PubMed

Gutiérrez, Angel J; Rubio, Carmen; Moreno, Isabel M; González, A Gustavo; Gonzalez-Weller, Dailos; Bencharki, Naouel; Hardisson, Arturo; Revert, Consuelo

2017-10-01

This paper describes the impact of mineral content on wines and assesses the potential health risk from consuming these wines from Canary Islands. The metal content (B, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Zn) of red wines belonging to different regions in the Canary Islands was determined by ICP-OES. The studied wine regions were Valle de la Orotava, Tacoronte-Acentejo, Ycoden-Daute-Isora, Abona and Valle de Güimar in Tenerife Island and only one in La Gomera and La Palma Islands. According to the content found, elements could be classified in two categories: the main group including Ca, K, Mg, Na, and the ''minor'' set consisting of B, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb and Zn. Once calculated the metal intake through red wines consumption, we can conclude that Canarian drinkers are not exposed to unsafe levels of the metals studied, actually, the safety intake limits (daily) ranges between 0.9% in Zn and 2% in Cu, for normal drinkers. And also it has been demonstrated the good quality of Canarian red wines and there is no reason for health concern through the THQ calculation being the highest values determined in La Gomera wines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Density functional theory study of lithium diffusion at the interface between olivine-type LiFePO4 and LiMnPO4

NASA Astrophysics Data System (ADS)

Shi, Jianjian; Wang, Zhiguo; Qing Fu, Yong

2016-12-01

Coating LiMnPO4 with a thin layer of LiFePO4 shows a better electrochemical performance than the pure LiFePO4 and LiMnPO4, thus it is critical to understand Li diffusion at their interfaces to improve the performance of electrode materials. Li diffusion at the (1 0 0)\\text{LiFeP{{\\text{O}}4}} //(1 0 0)\\text{LiMnP{{\\text{O}}4}} , (0 1 0)\\text{LiFeP{{\\text{O}}4}} //(0 1 0)\\text{LiMnP{{\\text{O}}4}} , and (0 0 1)\\text{LiFeP{{\\text{O}}4}} //(0 0 1)\\text{LiMnP{{\\text{O}}4}} interfaces between LiFePO4 and LiMnPO4 was investigated using density functional theory. The calculated diffusion energy barriers are 0.55 eV for Li to diffuse along the (0 0 1) interface, 0.44 and 0.49 eV for the Li diffusion inside the LiMnPO4 and along the (1 0 0) interface, respectively. When Li diffuses from the LiFePO4 to LiMnPO4 by passing through the (0 1 0) interfaces, the diffusion barriers are 0.45 and 0.60 eV for the Li diffusions in both sides. The diffusion barriers for Li to diffuse in LiMnPO4 near the interfaces decrease compared with those in the pure LiMnPO4. The calculated diffusion coefficient of Li along the (1 0 0) interface is in the range of 3.65  ×  10-11-5.28  ×  10-12 cm2 s-1, which is larger than that in the pure LiMnPO4 with a value of 7.5  ×  10-14 cm2 s-1. Therefore, the charging/discharging rate performance of the LiMnPO4 can be improved by surface coating with the LiFePO4.

Using elemental profiles and stable isotopes to trace the origin of green coffee beans on the global market.

PubMed

Santato, Alessandro; Bertoldi, Daniela; Perini, Matteo; Camin, Federica; Larcher, Roberto

2012-09-01

A broad elemental profile incorporating 54 elements (Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Re, Ir, Pt, Au, Hg, Tl, Pb, Bi and U) in combination with δ(2) H, δ(13) C, δ(15) N and δ(18) O was used to characterise the composition of 62 green arabica (Coffea arabica) and robusta (Coffea canephora) coffee beans grown in South and Central America, Africa and Asia, the four most internationally renowned areas of production. The δ(2) H, Mg, Fe, Co and Ni content made it possible to correctly assign 95% of green coffee beans to the appropriate variety. Canonical discriminant analysis, performed using δ(13) C, δ(15) N, δ(18) O, Li, Mg, P, K, Mn, Co, Cu, Se, Y, Mo, Cd, La and Ce correctly traced the origin of 98% of coffee beans. Copyright © 2012 John Wiley & Sons, Ltd.

Measuring the content of 17 elements in the flesh of Prunus cerasifera and its cultivars by ICP-MS.

PubMed

Shen, Jing; Xue, Hai-Yan; Li, Gai-Ru; Lu, Yi; Yao, Jun

2014-09-01

The present study compared the contents of inorganic elements in the pulp of purple, red, and yellow Prunus cerasifera with its cultivars. A method was established for the analysis of 17 kinds of trace elements (K, Ca, Mg, Na, Fe, Mn, Cu, Zn, Be, Li, Se, Sr, Cr, Pb, Cd, As and Hg) in the flesh of Prunus cerasifera by microwave digestion-ICP-MS. The detection method is simple and quick, yet shoes high precision and high sensitivity. The recovery rate of 17 elements ranged, from 93.5% to 110.4%. The analysis results showed that the contents of 17 elements in the flesh of purple, red, and yellow Prunus cerasifera and its cultivars are similar, containing extremely rich K elements (as high as 1 per thousand) and higher contents of Ca, Mg, Na, Fe and Mn. The contents of Cu, Zn, Li, Se, Sr and Cr are also present. The contents of Pb, Cd, As, Hg and other harmful element are either very low or not detectable. The experimental results for the study of trace elements in pulp of Prunus cerasifera and its cultivars provide empirical data for. future research in this area.

Investigation of the Influence of Selected Soil and Plant Properties from Sakarya, Turkey, on the Bioavailability of Trace Elements by Applying an In Vitro Digestion Model.

PubMed

Altundag, Huseyin; Albayrak, Sinem; Dundar, Mustafa S; Tuzen, Mustafa; Soylak, Mustafa

2015-11-01

The main aim of this study was an investigation of the influence of selected soil and plant properties on the bioaccessibility of trace elements and hence their potential impacts on human health in urban environments. Two artificial digestion models were used to determine trace element levels passing from soil and plants to man for bioavailability study. Soil and plant samples were collected from various regions of the province of Sakarya, Turkey. Digestive process is started by addition of soil and plant samples to an artificial digestion model based on human physiology. Bioavailability % values are obtained from the ratio of the amount of element passing to human digestion to element content of soil and plants. According to bioavailability % results, element levels passing from soil samples to human digestion were B = Cr = Cu = Fe = Pb = Li < Al < Ni < Co < Ba < Mn < Sr < Cd < Na < Zn < Tl, while element levels passing from plant samples to human digestion were Cu = Fe = Ni = Pb = Tl = Na = Li < Co < Al < Sr < Ba < Mn < Cd < Cr < Zn < B. It was checked whether the results obtained reached harmful levels to human health by examining the literature.

A General Method for High-Performance Li-Ion Battery Electrodes from Colloidal Nanoparticles without the Introduction of Binders or Conductive-Carbon Additives: The Cases of MnS, Cu(2-x)S, and Ge.

PubMed

Ha, Don-Hyung; Ly, Tiffany; Caron, Joseph M; Zhang, Haitao; Fritz, Kevin E; Robinson, Richard D

2015-11-18

In this work, we demonstrate a general lithium-ion battery electrode fabrication method for colloidal nanoparticles (NPs) using electrophoretic deposition (EPD). Our process is capable of forming robust electrodes from copper sulfide, manganese sulfide, and germanium NPs without the use of additives such as polymeric binders and conductive agents. After EPD, we show two postprocessing treatments ((NH4)2S and inert atmosphere heating) to effectively remove surfactant ligands and create a linked network of particles. The NP films fabricated by this simple process exhibit excellent electrochemical performance as lithium-ion battery electrodes. Additive-free Cu(2-x)S and MnS NP films show well-defined plateaus at ∼1.7 V, demonstrating potential for use as cathode electrodes. Because of the absence of additives in the NP film, this additive-free NP film is an ideal template for ex situ analyses of the particles to track particle morphology changes and deterioration as a result of Li ion cycling. To this end, we perform a size-dependent investigation of Cu(2-x)S NPs and demonstrate that there is no significant relationship between size and capacity when comparing small (3.8 nm), medium (22 nm), and large (75 nm) diameter Cu(2-x)S NPs up to 50 cycles; however, the 75 nm NPs show higher Coulombic efficiency. Ex situ TEM analysis suggests that Cu(2-x)S NPs eventually break into smaller particles (<10 nm), explaining a weak correlation between size and performance. We also report for the first time on additive-free Ge NP films, which show stable capacities for up to 50 cycles at 750 mAh/g.

Simulation of First-Charge Oxygen-Dimerization and Mn-Migration in Li-Rich Layered Oxides xLi 2MnO 3 ·(1 – x )Li MO 2 and Implications for Voltage Fade

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benedek, Roy; Iddir, Hakim

The instabilities of Li-rich layered oxide xLi 2MnO 3•(1-x)LiMO 2 (lithium-ion-battery cathode materials) during the first charge are investigated using first-principles dynamical simulation. To complement our earlier simulations for (x = 0.4, M = Ni 0.5Mn 0.5), we address here: pure Li 2MnO 3; small x; M compositions that include Co; a composite with Co spinel: Li 2MnO 3•Li 2M 2O 4; a Li 2MnO 3 slab. Lastly, we discuss how the threshold fraction f of Li 2(1-f)MnO 3 delithiation at which instabilities occur at the surface, fth(surface), differs from that in the bulk, f th(bulk). Approaches to inhibit voltagemore » fade are discussed.« less

Simulation of First-Charge Oxygen-Dimerization and Mn-Migration in Li-Rich Layered Oxides xLi 2MnO 3 ·(1 – x )Li MO 2 and Implications for Voltage Fade

DOE PAGES

Benedek, Roy; Iddir, Hakim

2017-03-08

The instabilities of Li-rich layered oxide xLi 2MnO 3•(1-x)LiMO 2 (lithium-ion-battery cathode materials) during the first charge are investigated using first-principles dynamical simulation. To complement our earlier simulations for (x = 0.4, M = Ni 0.5Mn 0.5), we address here: pure Li 2MnO 3; small x; M compositions that include Co; a composite with Co spinel: Li 2MnO 3•Li 2M 2O 4; a Li 2MnO 3 slab. Lastly, we discuss how the threshold fraction f of Li 2(1-f)MnO 3 delithiation at which instabilities occur at the surface, fth(surface), differs from that in the bulk, f th(bulk). Approaches to inhibit voltagemore » fade are discussed.« less

A simplified soil extraction sequence to monitor the main and trace element speciation in soil after compost and mineral fertilizer additions upon the composition of wheat grains

NASA Astrophysics Data System (ADS)

Sager, Manfred; Erhart, Eva

2016-04-01

High quality biological waste treatment aims at producing compost in order to maintain a clean environment and to sustain soil organic carbon levels. Fertilization with compost as a source of organic carbon, nutrients, and accessory elements, as well as fertilization with mineral N- and PK fertilizer have been tested in a field experiment on a calcaric Fluvisol in the Danube wetlands, at 4 levels each. Yields of wheat were recorded, and grains and soils were sampled from each treatment, and analyzed for main and trace element composition. The corresponding soils were characterized by mobile phases, obtained by leaching with 0,16M acetic acid to cover exchangeables plus carbonates, and subsequently by 0,1M oxalate buffer pH 3 to dissolve the pedogenic oxides. Total amounts were obtained from digests with perchloric- nitric-hydrofluoric acid. For quasi-total amounts, aqua regia was replaced by pressure decomposition with KClO3 in dilute nitric acid. The proposed extraction sequence permits to analyze and interpret soil for main elements, trace elements, nutrients and anions simultaneously. Factor analyses of soil extracts obtained from dilute acetic acid revealed Ba-Be-Cd-Cu-Li-S (traces), Ca-Mg-Mn (main carbonates), Al-Fe-B, Y, and P-K (nutrients) as chemically feasible principal components. Subsequent soil extracts from oxalate contained Al-B-Co-K-Na-Pb-Si-V-S (maybe acid silicate weathering), Cr-Li-Ni-Sr-Ti (maybe basic silicate weathering), Be-Cu-Fe-P, Co-Mg-Mn-Zn (Mn-oxides) and Ba-Sc as principal components. Factor analyses of total element data distinguished the principal components Ce-La-Li-Sc-Y-P (rare earths), Al-Ca-Fe-K-Mg-Na-P (main elements), Cd-Co-Cr-Cu-Ni-Zn (trace elements), As-Pb (contaminants), Ba-Mn-Sr, and Ti, which looks chemically feasible also. Factor analyses of those soil fractions which presumably form the main fractions of exchangeables, carbonates, pedogenic oxides and silicates, showed no cross connections, except for P. Oxalate-soluble Fe together with P and S was independent from oxalate-soluble Al-Mn-Si. In the crops, all element levels were within a non-contaminated and non-deficient range, therefore correlations with concentrations as well as loads in the wheat grains where largely not pronounced. Maximum correlations between plant and soil data were obtained with Li and Be. The load data (concentration times yield, given in g/ha) were much more intercorrelated than the concentrations. Regarding the same element, correlation coefficients between loads and respective concentrations were larger than 0,800 for Al, Ba, Cd, Co, Cr, Li, Mo, Na, Ni, Se, and Sr, which means the transfer remained independent from the load. In case of Ca, Mg, P, S, Zn, however, correlation coefficients between loads and concentrations were < 0,500, thus the transfer was not constant because of obvious metabolic influences. The proposed method of soil characterization was applied at a field trial here for the first time, and offers new possibilities of intercorrelations between plant uptake and geochemical soil fractions.

First-charge instabilities of layered-layered lithium-ion-battery materials.

PubMed

Croy, Jason R; Iddir, Hakim; Gallagher, Kevin; Johnson, Christopher S; Benedek, Roy; Balasubramanian, Mahalingam

2015-10-07

Li- and Mn-rich layered oxides with composition xLi2MnO3·(1 -x)LiMO2 enable high capacity and energy density Li-ion batteries, but suffer from degradation with cycling. Evidence of atomic instabilities during the first charge are addressed in this work with X-ray absorption spectroscopy, first principles simulation at the GGA+U level, and existing literature. The pristine material of composition xLi2MnO3·(1 -x)LiMn0.5Ni0.5O2 is assumed in the simulations to have the form of LiMn2 stripes, alternating with NiMn stripes, in the metal layers. The charged state is simulated by removing Li from the Li layer, relaxing the resultant system by steepest descents, then allowing the structure to evolve by molecular dynamics at 1000 K, and finally relaxing the evolved system by steepest descents. The simulations show that about ¼ of the oxygen ions in the Li2MnO3 domains are displaced from their original lattice sites, and form oxygen-oxygen bonds, which significantly lowers the energy, relative to that of the starting structure in which the oxygen sublattice is intact. An important consequence of the displacement of the oxygen is that it enables about ⅓ of the (Li2MnO3 domain) Mn ions to migrate to the delithiated Li layers. The decrease in the coordination of the Mn ions is about twice that of the Ni ions. The approximate agreement of simulated coordination number deficits for Mn and Ni following the first charge with analysis of EXAFS measurements on 0.3Li2MnO3·0.7LiMn0.5Ni0.5O2 suggests that the simulation captures significant features of the real material.

Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; An, Yongling; Zhai, Wei

2015-10-15

Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviationmore » in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.« less

Synthesis and structural stability of Cr-doped Li2MnSiO4/C cathode materials by solid-state method

NASA Astrophysics Data System (ADS)

Cheng, Hong-Mei; Zhao, Shi-Xi; Wu, Xia; Zhao, Jian-Wei; Wei, Lei; Nan, Ce-Wen

2018-03-01

The crystal structure of the Li2MnSiO4 cathode material would collapse during the charge and discharge process because of that the Mn-O coordination polyhedron changed from [MnO4] into [MnO6] in the process of Mn+2 to Mn+4, but the Cr element could remain [CrO4] crystal ligand from Cr+2 to Cr+4, so Cr element substitution was used to improve the structural stability of the Li2MnSiO4 cathode material. In this work, Li2Mn1-xCrxSiO4/C nanocomposites were synthesized by solid-state method. XRD, SEM and TEM observations show that the as-prepared Li2Mn1-xCrxSiO4/C materials presents an orthorhombic crystal structure (S.G. Pmn21), the particle size of Li2Mn1-xCrxSiO4/C powder ranges from 50 to 100 nm. The XRD and XPS results indicate that Cr+2 is successfully doped into Li2MnSiO4 lattice and has well compatibility with Li2MnSiO4. The electrochemical results display that Li2Mn92.5%Cr7.5%SiO4/C exhibits significantly enhanced cycle stability and discharge capability. The initial discharge capacity of the Li2Mn92.5%Cr7.5%SiO4/C sample is 255 mAh g-1, and the discharge capacity was still about 60 mAh g-1 after 50 cycles. Furthermore, the XRD patterns, TEM images and Raman analysis reveal that the Cr doping enhances the structural stability of Li2Mn1-xCrxSiO4/C and improves the electrochemical activity of the cathode. Thus, the Li2Mn92.5%Cr7.5%SiO4/C have shown potential applications for lithium ion batteries.

Environmental exposures of trace elements assessed using keratinized matrices from patients with chronic kidney diseases of uncertain etiology (CKDu) in Sri Lanka.

PubMed

Diyabalanage, Saranga; Fonseka, Sanjeewani; Dasanayake, D M S N B; Chandrajith, Rohana

2017-01-01

An alarming increase in chronic kidney disease with unknown etiology (CKDu) has recently been reported in several provinces in Sri Lanka and chronic exposures to toxic trace elements were blamed for the etiology of this disease. Keratinized matrices such as hair and nails were investigated to determine the possible link between CKDu and toxic element exposures. Elements Li, B, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Ba, Hg and Pb of hair and nails of patients and age that matched healthy controls were determined with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The results showed that trace element contents in the hair of patients varies in the order of Zn>Fe>Al>Mn>Cu>Ba>Sr>Ni>Pb>Cr>B>Hg>Se>Mo>Co>As>Li>Cd while Fe>Al>Zn>Ni>Cu>Mn>Cr>Ba>Sr>B>Pb>Se>Mo>Co>Hg>Li>As>Cd in nail samples. The hair As levels of 0.007-0.165μgg -1 were found in CKDu subjects. However, no significant difference was observed between cases and controls. The total Se content in hair of CKDu subjects ranged from 0.043 to 0.513μgg -1 while it was varied from 0.031 to 1.15μgg -1 in controls. Selenium in nail samples varied from 0.037μgg -1 to 4.10μgg -1 in CKDu subjects and from 0.042μgg -1 to 2.19μgg -1 in controls. This study implies that substantial proportions of Sri Lankan population are Se deficient irrespective of gender, age and occupational exposure. Although some cutaneous manifestations were observed in patient subjects, chemical analyses of hair and nails indicated that patients were not exposed to toxic levels of arsenic or the other studied toxic elements. Therefore the early suggested causative factors such as exposure to environmental As and Cd, can be ruled out. Copyright © 2016 Elsevier GmbH. All rights reserved.

Expert Assessment of Advanced Power Sources

DTIC Science & Technology

2007-07-01

including [13] LiCo1-yNiyO2 , LiNiO2, LiMnO2, LiMn2O4, LiV2O5 and LiFePO4 . The last compound, lithium iron phosphate [19], is attractive as iron is...cheaper and more environmentally friendly than cobalt, nickel or manganese. Commercial development of a lithium ion battery based on LiFePO4 is...electrochemical performance evaluated. Materials studied include: LiV2O5 and other vanadium oxides, LiCoO2, LiMnO2, LiMn2O4 and LiFePO4 . 3-D

Negative electrodes for lithium cells and batteries

DOEpatents

Vaughey, John T.; Fransson, Linda M.; Thackeray, Michael M.

2005-02-15

A negative electrode is disclosed for a non-aqueous electrochemical cell. The electrode has an intermetallic compound as its basic structural unit with the formula M.sub.2 M' in which M and M' are selected from two or more metal elements including Si, and the M.sub.2 M' structure is a Cu.sub.2 Sb-type structure. Preferably M is Cu, Mn and/or Li, and M' is Sb. Also disclosed is a non-aqueous electrochemical cell having a negative electrode of the type described, an electrolyte and a positive electrode. A plurality of cells may be arranged to form a battery.

Coating effect of LiFePO4 and Al2O3 on Li1.2Mn0.54Ni0.13Co0.13O2 cathode surface for lithium ion batteries

NASA Astrophysics Data System (ADS)

Seteni, Bonani; Rapulenyane, Nomasonto; Ngila, Jane Catherine; Mpelane, Siyasanga; Luo, Hongze

2017-06-01

Lithium-manganese-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by combustion method, and then coated with nano-sized LiFePO4 and nano-sized Al2O3 particles via a wet chemical process. The as-prepared Li1.2Mn0.54Ni0.13Co0.13O2, LiFePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 and Al2O3-coated Li1.2Mn0.54Ni0.13Co0.13O2 are characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The scanning electron microscopy shows the agglomeration of the materials and their nanoparticle size ∼100 nm. The transmission electron microscopy confirms that LiFePO4 forms a rough mat-like surface and Al2O3 remain as islandic particles on the surface of the Li1.2Mn0.54Ni0.13Co0.13O2 material. The Li1.2Mn0.54Ni0.13Co0.13O2 coated with LiFePO4 and Li1.2Mn0.54Ni0.13Co0.13O2 coated with Al2O3 exhibits improved electrochemical performance. The initial discharge capacity is enhanced to 267 mAhg-1 after the LiFePO4 coating and 285 mAhg-1 after the Al2O3 coating compared to the as-prepared Li1.2Mn0.54Ni0.13Co0.13O2 material that has an initial discharge capacity of 243 mAhg-1. Galvanostatic charge-discharge tests at C/10 display longer activation of Li2MnO3 phase and higher capacity retention of 88% after 20 cycles for Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3 of 80% after 20 cycles and LMNC of 80% after 20 cycles. Meanwhile Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 also shows higher rate capability compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3.

Simulation and analysis of stress in a Li-ion battery with a blended LiMn2O4 and LiNi0.8Co0.15Al0.05O2 cathode

NASA Astrophysics Data System (ADS)

Dai, Yiling; Cai, Long; White, Ralph E.

2014-02-01

Stress generation due to Li ion insertion into/extraction from LiMn2O4 particles is studied with a mathematical model for a lithium ion battery with pure LiMn2O4 or mixed LiMn2O4 and LiNi0.8Co0.15Al0.05O2 cathode. The simulated stress profile in a pure LiMn2O4 electrode shows nonuniformity across the positive electrode. The cathode blended model predicts that the stress generated in the LiMn2O4 particles is reduced at the end of discharge due to adding LiNi0.8Co0.15Al0.05O2 to the cathode. The effect of the variation in the blend ratio on the stress generation is also investigated.

Modified structural characteristics and enhanced electrochemical properties of oxygen-deficient Li2MnO3-δ obtained from pristine Li2MnO3

NASA Astrophysics Data System (ADS)

Tan, Xiao; Liu, Rui; Xie, Congxin; Shen, Qiang

2018-01-01

Lithium-rich manganese(IV) oxide Li2MnO3 has hardly any activity as the cathode active substance of lithium-ion batteries (LIBs) but its reversible capacity can be greatly improved by introducing oxygen deficiencies. After the solid-state heat treatment of nanocrystalline Li2MnO3 by sodium borohydride (NaBH4), the resulting Li2MnO3-δ crystallites comparatively acquire distinguishable appearances in color and shape and slight differences in surface composition and lattice structure. As a LIB cathode within the potential range of 2.5-4.7 V, at 20 mA g-1 pristine Li2MnO3 gives the specific discharge capacities of 3.3, 5.0 and 7.4 mAh·g-1 in the 1st, 10th and 100th cycles, while the derivative Li2MnO3-δ delivers the relatively high values of 64.8, 103.8 and 140.2 mAh·g-1 in the 1st, 10th and 120th cycles, respectively. Aside from the similar phenomenon of gradual electrochemical activation, substituting Li2MnO3-δ for Li2MnO3 means the great enhancements of charge-transfer ability and electrochemical performances. Especially, the cationic-anionic redox mechanisms of Li2MnO3 and Li2MnO3-δ are similar to each other, suggesting a possible solution to prepare high-performance xLi2MnO3-δ·(1-x)LiMO2 solid solutions for application purposes.

Fungal Pretreatment of Sweet Sorghum Bagasse with Combined CuSO4-Gallic Acid Supplement for Improvement in Lignin Degradation, Selectivity, and Enzymatic Saccharification.

PubMed

Mishra, Vartika; Jana, Asim K

2017-09-01

Sweet sorghum (Sorghum sp.) has high biomass yield. Hydrolysis of lignocellulosic sweet sorghum bagasse (SSB) to fermentable sugar could be useful for manufacture of biofuel or other fermentation products. Pretreatment of lignocellulosic biomass to degrade lignin before enzymatic hydrolysis is a key step. Fungal pretreatment of SSB with combined CuSO 4 -gallic acid supplements in solid-state fermentation (SSF) to achieve higher lignin degradation, selectivity value (SV), and enzymatic hydrolysis to sugar was studied. Coriolus versicolor was selected due to high activities of ligninolytic enzymes laccase, lignin peroxidase (LiP), manganese peroxidase (MnP), polyphenol oxidase (PPO), and arylalcohol oxidase (AAO) and low activities of cellulolytic enzymes CMCase, FPase, and β-glucosidase with high lignin degradation and SV in 20 days. CuSO 4 /gallic acid increased the activities of ligninolytic enzymes resulting in enhanced lignin degradations and SVs. Cumulative/synergistic effect of combined supplements further increased the activities of laccase, LiP, MnP, PPO, and AAO by 7.6, 14.6, 2.67, 2.06, and 2.15-folds, respectively (than control), resulting in highest lignin degradation 31.1 ± 1.4% w/w (1.56-fold) and SV 2.33 (3.58-fold). Enzymatic hydrolysis of pretreated SSB yielded higher (~2.2 times) fermentable sugar. The study showed combined supplements can improve fungal pretreatment of lignocellulosic biomass. XRD, SEM, FTIR, and TGA/DTG of SSB confirmed the results.

Electrochemical performance of all-solid-state Li batteries based LiMn 0.5Ni 0.5O 2 cathode and NASICON-type electrolyte

NASA Astrophysics Data System (ADS)

Xie, J.; Imanishi, N.; Zhang, T.; Hirano, A.; Takeda, Y.; Yamamoto, O.; Zhao, X. B.; Cao, G. S.

LiNi 0.5Mn 0.5O 2 thin films have been deposited on the NASICON-type glass ceramics, Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATSP), by radio frequency (RF) magnetron sputtering followed by annealing. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. All-solid-state Li/PEO 18-Li(CF 3SO 2) 2N/LATSP/LiNi 0.5Mn 0.5O 2/Au cells are fabricated using the LiNi 0.5Mn 0.5O 2 thin films and the LATSP electrolyte. The electrochemical performance of the cells is investigated by galvanostatic cycling, cyclic voltammetry (CV), potentiostatic intermittent titration technique (PITT) and electrochemical impedance spectroscopy (EIS). Interfacial reactions between LiNi 0.5Mn 0.5O 2 and LATSP occur at a temperature as low as 300 °C with the formation of Mn 3O 4, resulting in an increased obstacle for Li-ion diffusion across the LiNi 0.5Mn 0.5O 2/LATSP interface. The electrochemical performance of the cells is limited by the interfacial resistance between LATSP and LiNi 0.5Mn 0.5O 2 as well as the Li-ion diffusion kinetics in LiNi 0.5Mn 0.5O 2 bulk.

PIXE and ICP-MS Analysis of Andrographis Paniculata Medicinal Plant

NASA Astrophysics Data System (ADS)

Chandrasekhar Rao, J.; Naidu, B. G.; Sarita, P.; Srikanth, S.; Naga Raju, G. J.

2017-08-01

The concentrations of elements Li, Be, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Ag, Cd, Ba, Pb and U in Andrographis Paniculata medicinal plant used in the treatment of Diabetes Mellitus were determined by using Particle Induced X-ray Emission (PIXE) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) techniques. This plant was collected from four different geographical locations in Andhra Pradesh, India in order to assess the regional variation of elemental concentrations. Appreciable levels of K, Ca, Cr, Mn, Cu and Zn determined in this plant can be correlated to the antidiabetic property of Andrographis Paniculata since these elements are known to regulate and potentiate insulin action. Presence of toxic elements As, Cd and Pb necessitates the adoption of precautionary measures while prescribing dosage of the herbal medicine prepared from this plant for the treatment diabetes mellitus.

Thermal and electrochemical behavior of Cu{sub 4−x}Li{sub x}S{sub 2} (x=1, 2, 3) phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Erica M.; Poudeu, Pierre F.P., E-mail: ppoudeup@umich.edu

Several compositions of the Cu{sub 4−x}Li{sub x}S{sub 2} (x=1, 2, 3) series were synthesized via solid-state reaction of the elements. The structural stability at various temperatures and the effect of Li:Cu ratio on the thermal conductivity and the electrochemical performance of Cu{sub 4−x}Li{sub x}S{sub 2}/Li half-cells during charge–discharge process were investigated. Differential scanning calorimetry (DSC) measurements showed a sharp endothermic peak at 140 °C for Cu{sub 4−x}Li{sub x}S{sub 2} samples with x=1 and 2, which is ascribed to a structural phase transition. X-ray diffraction (XRD) measurements on various Cu{sub 4−x}Li{sub x}S{sub 2} samples at temperatures below and above 140 °Cmore » indicated a structural phase transition from the room temperature low-symmetry structure to the high temperature cubic structure of Cu{sub 2}S. The thermal conductivity of Cu{sub 4−x}Li{sub x}S{sub 2} samples decreases with decreasing Cu:Li ratio and with increasing temperature. The thermal conductivity of Cu{sub 4−x}Li{sub x}S{sub 2} samples at room temperature decreases from 1.2 W/m K for Cu:Li=3:1 to 0.7 W/m K for Cu:Li=1:3. Cyclic voltammetry of Cu{sub 4−x}Li{sub x}S{sub 2}/Li half-cells showed that high discharge capacity (165 mA h g{sup −1}) and stable reversible charge–discharge process is observed for Cu:Li=2:2, whereas other Cu:Li ratios lead to low discharge capacity and poor reversibility. The electrochemical behavior of Cu{sub 4−x}Li{sub x}S{sub 2}/Li half-cells is rationalized by taking into account the competing reactions of Li{sup +} ions with CuS and Cu{sub 2}S during discharge. - Graphical abstract: Tuning Li content in Cu{sub 4−x}Li{sub x}S{sub 2}/Li half-cells to maintain a Cu/Li ratio equal to unity affords maximum capacity and high stability of the charge–discharge process. - Highlights: • Cu:Li ratio strongly influenced crystal structure and properties of Cu{sub 4-x}Li{sub x}S{sub 2}. • Compositions with x = 1 and 2 undergo structural transformation at above 140 °C. • Thermal conductivity of Cu{sub 4-x}Li{sub x}S{sub 2} phases increases with decreasing Cu:Li ratio. • Stability of Cu{sub 4-x}Li{sub x}S{sub 2}/Li half-cells decreases with Cu:Li ratio. • Initial charge capacity of Cu{sub 4-x}Li{sub x}S{sub 2}/Li half-cells increases with Cu:Li ratio.« less

Mechanochemical Synthesis of Li2MnO3 Shell/LiMO2 (M = Ni, Co, Mn) Core-Structured Nanocomposites for Lithium-Ion Batteries

PubMed Central

Noh, Jae-Kyo; Kim, Soo; Kim, Haesik; Choi, Wonchang; Chang, Wonyoung; Byun, Dongjin; Cho, Byung-Won; Chung, Kyung Yoon

2014-01-01

Core/shell-like nanostructured xLi2MnO3·(1−x)LiMO2 (M = Ni, Co, Mn) composite cathode materials are successfully synthesized through a simple solid-state reaction using a mechanochemical ball-milling process. The LiMO2 core is designed to have a high-content of Ni, which increases the specific capacity. The detrimental surface effects arising from the high Ni-content are countered by the Li2MnO3 shell, which stabilizes the nanoparticles. The electrochemical performances and thermal stabilities of the synthesized nanocomposites are compared with those of bare LiMO2. In particular, the results of time-resolved X-ray diffraction (TR-XRD) analyses of xLi2MnO3·(1−x)LiMO2 nanocomposites as well as their differential scanning calorimetry (DSC) profiles demonstrate that the Li2MnO3 shell is effective in stabilizing the LiMO2 core at high temperatures, making the nanocomposites highly suitable from a safety viewpoint. PMID:24784478

Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

PubMed

Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

2015-11-16

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

High-temperature X-ray diffraction study of crystallization and phase segregation on spinel-type lithium manganese oxides

NASA Astrophysics Data System (ADS)

Komaba, Shinichi; Yabuuchi, Naoaki; Ikemoto, Sachi

2010-01-01

To study crystallization process of spinel-type Li 1+xMn 2-xO 4, in-situ high-temperature X-ray diffraction technique (HT-XRD) was utilized for the mixture consisting of Li 2CO 3 and Mn 2O 3 as starting material in the temperature range of 25-700 °C. In-situ HT-XRD analysis directly revealed that crystallization process of Li 1+xMn 2-xO 4 was significantly affected by the difference in the Li/Mn molar ratio in the precursor. Single phase of stoichiometric LiMn 2O 4 formed at 700 °C. The formation of single phase of spinel was achieved at the lower temperature than the stoichiometric sample as Li/Mn molar ratio in the precursor increased. Lattice parameter of the stoichiometric LiMn 2O 4 at 25 °C was 8.24 Å and expanded to 8.31 Å at 700 °C, which corresponds to the approximately 3% expansion in the unit cell volume. From the slope of the lattice parameter change as a function of temperatures, linear thermal expansion coefficient of the stoichiometric LiMn 2O 4 was calculated to be 1.2×10 -5 °C -1 in this temperature range. When the Li/Mn molar ratio in Li 1+xMn 2-xO 4 increased ( x > 0.1), the spinel phase segregated into the Li 1+yMn 2-yO 4 ( x > y) and Li 2MnO 3 during heating, which involved the oxygen loss from the materials. During the cooling process from 700 °C, and the segregated phase merged into Li 1+xMn 2-xO 4 with oxygen incorporation. Such trend directly observed by in-situ HT-XRD was supported by thermal gravimetric analysis as reversible weight (oxygen) loss/gain at higher temperature (500-700 °C).

On the observation of a huge lattice contraction and crystal habit modifications in LiMn 2O 4 prepared by a fuel assisted solution combustion

NASA Astrophysics Data System (ADS)

Ragavendran, K.; Sherwood, D.; Vasudevan, D.; Emmanuel, Bosco

2009-08-01

Two batches of poly-crystalline lithium manganate were prepared by a fuel assisted solution combustion method. LiMn 2O 4(S) was prepared using starch as the fuel and LiMn 2O 4(P) was prepared using poly vinyl alcohol (PVA) as the fuel. XRD studies indicated a significant and consistent shift in the 2 θ values of all the hkl peaks to higher values in LiMn 2O 4(P) compared to LiMn 2O 4(S) indicating a lattice contraction in the former. TG/DTA studies indicated a higher formation temperature (∼25 °C higher) for LiMn 2O 4(P). The higher formation temperature most likely promotes the oxidation of some Mn 3+ to Mn 4+ with a lower ionic radius causing a lattice contraction. This hypothesis is confirmed through XPS studies which indicated the presence of a higher fraction of Mn 4+ in LiMn 2O 4(P) than that present in LiMn 2O 4(S). A crystal shape algorithm was used to generate the crystal habits of lithium manganate from their XRD data leading to an understanding on the exposed hkl planes in these materials. From the atomic arrangement on the exposed hkl planes it is predicted that LiMn 2O 4(P) would be less prone to manganese dissolution and hence would possess a higher cycle life when compared to LiMn 2O 4(S).

Surface studies of Li-ion and Mg battery electrodes

NASA Astrophysics Data System (ADS)

Esbenshade, Jennifer

This dissertation focuses on studies of the surfaces of both Li-ion and Mg-ion battery electrodes. A fundamental understanding of processes occurring at the electrode surface is vital to the development of advanced battery systems. Additionally, modifications to the electrode surfaces are made and further characterized for improved performance. LiMn2O4 Cathodes for Li-ion Batteries: Effect of Mn in electrolyte on anode and Au coating to minimize dissolution: LiMn2O4 (LMO) is known to dissolve Mn ions with cycling. This section focuses on both the effect of the dissolution of Mn2+ into the electrolyte as well as Au coating on the LMO to improve electrochemical performance. Electrochemical quartz crystal microbalance (EQCM) was used to monitor changes in mass on the anode, SEM and AES were used to observe changes in surface morphology and chemical composition, and potentiostatic voltammetry was used to monitor charge and discharge capacity. The effect of Cu2+ addition in place of Mn2+ was also studied, as Cu is known to form an underpotential deposition (UPD) monolayer on Au electrodes. Following this, LMO particles were coated with a Au shell by a simple and scalable electroless deposition for use as Li-ion battery cathodes. The Au shell was intended to limit the capacity fade commonly seen with LMO cathodes by reducing the dissolution of Mn. Characterization by SEM, TEM, EELS, and AFM showed that the Au shell was approximately 3 nm thick. The Au shell prevented much of the Mn from dissolving in the electrolyte with 82% and 88% less dissolved Mn in the electrolyte at room temperature and 65 ºC, respectively, as compared to the uncoated LMO. Electrochemical performance studies with half cells showed that the Au shell maintained a higher discharge capacity over 400 cycles by nearly 30% with 110 mA hr g-1 for the 400th cycle as compared to a commercial LMO at 85 mA hr g-1. Similarly, the capacity fade was reduced in full cells: the coated LMO had 47% greater capacity after 400 cycles over the control. Dimensionally Controlled Lithiation of Thin Film and Multilayer Conversion Li-ion Battery Anodes: Oxide conversion reactions are an alternative approach for high capacity Li-ion batteries, but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. The morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. In this section, a model electrode is used with alternating layers of Cr and CrOx to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials. Following the Cr/CrOx study, the next step was to study intermetallics which can electrochemically alloy to Li4.4M (M = Si, Ge, Sn, etc.), providing order-of-magnitude increases in energy density. The energy density of Si may be combined with the structural reversibility of an intercalation material using a Si/metal silicide multilayer (ML). In operando XR confirms the ML's structural reversibility during Li insertion and extraction, despite an overall 3.3-fold vertical expansion. The ML electrodes also show enhanced long-term cyclability and rate capabilities relative to a comparable Si thin film electrode. This intercalation behavior found by dimensionally constraining Si lithiation promises applicability to a range of conversion reactions. Improving Electrodeposition of Mg through an Open Circuit Potential Hold: In this section, in situ XRD, XPS, SEM and electrochemical methods were used to interrogate the mechanism of Mg electrodeposition from PhMgCl/AlCl3 (APC) and EtMgCl electrolytes. An open circuit potential (OCP) pause following Mg deposition led to retained enhancement of Mg deposition and stripping kinetics along with lowered overpotentials for both. In situ XRD demonstrated that the OCP pause led to a more polycrystalline deposits relative to that without the pause, while SEM presented micrographs that showed smaller deposits with an OCP hold. The improvement is attributed to an 'enhancement layer' that formed on the electrode during the OCP hold. Analysis of XPS data suggests that this 'enhancement layer' consists of Mg and Cl retained on the electrode surface, possibly following electrode depassivation.

Enhanced recovery of valuable metals from spent lithium-ion batteries through optimization of organic acids produced by Aspergillus niger.

PubMed

Bahaloo-Horeh, Nazanin; Mousavi, Seyyed Mohammad

2017-02-01

In the present study, spent medium bioleaching method was performed using organic acids produced by Aspergillus niger to dissolve Ni, Co, Mn, Li, Cu and Al from spent lithium-ion batteries (LIBs). Response surface methodology was used to investigate the effects and interactions between the effective factors of sucrose concentration, initial pH, and inoculum size to optimize organic acid production. Maximum citric acid, malic acid, and gluconic acid concentrations of 26,478, 1832.53 and 8433.76ppm, respectively, and a minimum oxalic acid concentration of 305.558ppm were obtained under optimal conditions of 116.90 (gl -1 ) sucrose concentration, 3.45% (vv -1 ) inoculum size, and a pH value of 5.44. Biogenically-produced organic acids are used for leaching of spent LIBs at different pulp densities. The highest metal recovery of 100% Cu, 100% Li, 77% Mn, and 75% Al occurred at 2% (wv -1 ) pulp density; 64% Co and 54% Ni recovery occurred at 1% (wv -1 ) pulp density. The bioleaching of metals from spent LIBs can decrease the environmental impact of this waste. The results of this study suggest that the process can be used for large scale industrial purposes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhuo, Zengqing; Olalde-Velasco, Paul.; Chin, Timothy

We performed a comparative study of the soft x-ray absorption spectroscopy of the LiMn2O4 and Li1.15Mn1.85O4 electrode materials with a quantitative analysis of the Mn oxidation states. The revealed redox evolution of Mn upon the electrochemical cycling clarifies the effect of the excess Li in the materials, which naturally explains the different electrochemical performance. The spectral analysis perfectly agrees with the different initial cycling capacities of the two materials. The results show unambiguously that Mn3+ starts to dominate the electrode surface after only one cycle. More importantly, the data show that, while LiMn2O4 electrodes follow the nominal Mn redox evolution,more » the formation of Mn3+ on the electrode surface is largely retarded for the Li1.15Mn1.85O4 during most of the electrochemical process. Such a different surface Mn redox behavior leads to differences in the detrimental effects of Mn2+ formation on the surface, which is observed directly after only two cycles. Our results provide strong evidence that a key effect of the (bulk) excess Li doping is actually due to processes on the electrode surfaces.« less

Effect of excess lithium in LiMn2O4 and Li1.15Mn1.85O4 electrodes revealed by quantitative analysis of soft X-ray absorption spectroscopy

DOE PAGES

Zhuo, Zengqing; Olalde-Velasco, Paul.; Chin, Timothy; ...

2017-02-27

We performed a comparative study of the soft x-ray absorption spectroscopy of the LiMn2O4 and Li1.15Mn1.85O4 electrode materials with a quantitative analysis of the Mn oxidation states. The revealed redox evolution of Mn upon the electrochemical cycling clarifies the effect of the excess Li in the materials, which naturally explains the different electrochemical performance. The spectral analysis perfectly agrees with the different initial cycling capacities of the two materials. The results show unambiguously that Mn3+ starts to dominate the electrode surface after only one cycle. More importantly, the data show that, while LiMn2O4 electrodes follow the nominal Mn redox evolution,more » the formation of Mn3+ on the electrode surface is largely retarded for the Li1.15Mn1.85O4 during most of the electrochemical process. Such a different surface Mn redox behavior leads to differences in the detrimental effects of Mn2+ formation on the surface, which is observed directly after only two cycles. Our results provide strong evidence that a key effect of the (bulk) excess Li doping is actually due to processes on the electrode surfaces.« less

Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

NASA Astrophysics Data System (ADS)

Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

2002-12-01

There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

(sup 6)Li and (sup 7)MAS NMR and In Situ X-Ray Diffraction Studies of Lithium Manganate Cathode Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Young Joo; Wang, Francis; Grey, Clare P.

{sup 6}Li MAS NMR spectra of lithium manganese oxides with differing manganese oxidation states (LiMn{sub 2}O{sub 4}, Li{sub 4}Mn{sub 5}O{sub 12}, Li{sub 2}Mn{sub 4}O{sub 9}, and Li{sub 2}Mn{sub 2}O{sub 4}) are presented. Improved understanding of the lithium NMR spectra of these model compounds is used to interpret the local structure of the Li{sub x}Mn{sub 2}O{sub 4} cathode materials following electrochemical Li{sup +} deintercalation to various charging levels. In situ x-ray diffraction patterns of the same material during charging are also reported for comparison. Evidence for two-phase behavior for x <0.4 (Li{sub x}Mn{sub 2}O{sub 4}) is seen by both NMR andmore » diffraction.« less

Marine ferromanganese deposits as a source of rare metals for high- and green-tech applications: Comparison with land-based deposits

NASA Astrophysics Data System (ADS)

Hein, J. R.; Conrad, T. A.; Koschinsky, A.

2011-12-01

Marine ferromanganese (Fe-Mn) crusts are strongly enriched relative to the lithosphere in many rare and strategic metals, including Te, Co, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REE). Fe-Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, and REY. Relative to Fe-Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo. The metals are sorbed from seawater onto the Fe and Mn phases, and also from sediment pore waters for nodules. An electrochemical model describes a first-order process for acquisition of metals from seawater, with positively charged ions sorbed onto the negative charged surface of MnO2 and negatively charged and neutral ions in seawater sorbed on the slightly positive charged FeO(OH) surface. Second-order processes include surface oxidation (e.g., Co, Pt, Te, Ce, Tl), substitution, and precipitation of discrete phases. The metals most enriched in these marine deposits are essential for a wide variety of high- and green-tech applications. Over the past few years, the global market for many of them has been supplied from one or two major sources. Because of increased competition for resources from rapidly expanding economies (i.e. China, India, Brazil), supplies may not meet demands. Deep-ocean deposits may offer a partial solution to these projected shortages, but marine deposits have not been compared in terms of grade and tonnage with land-based deposits. Here we compare data for the Clarion-Clipperton Fe-Mn Nodule Zone (CCZ) in the NE Pacific and the central Pacific Fe-Mn crust zone (PCZ) with the global land-based reserves. Nodules in the CCZ have 1.1 times more Mn, 1.4 times more Te, 1.85 times more Ni, 3.2 times more Co, and 4 times more Y than the entire global land-based reserves for those metals. Metals in CCZ nodules as a percent of the total global land-based reserves are Cu 22%, Mo 63%, W 21%, Li 19%, Nb 13%, and REE 11%. Fe-Mn crusts in the PCZ have 3.8 times more Co, 3.5 times more Y, and an incredible 9 times more Te than the entire land-based reserves. Metals in PCZ crusts as a percent of the total global land-based reserves are Bi 47%, REO 13%, Nb 13%, and W 11%. CCZ nodules and PCZ crusts are compared with the two largest existing land-based REE mines, Mountain Pass (MP) in USA and Bayan Obo (Obo) in China. The land-based deposits are higher grade but lower tonnage (MP 0.3x108 tons at 7.5% total REEs as oxides (TREO); Obo, 0.5x108 tons at 6% TREO), compared to the CCZ (211x108 tons at 0.10% TREO) and PCZ (75.3x108 tons at 0.3% TREO). These grades and tonnages correspond to tons of TREO of 4.7x107 Obo, 2.6x106 MP; 2.1x107 CCZ, and 2.1x107 PCZ. Both land-based deposits have <1% heavy REE, whereas the CCZ has 10% HREE and the PCZ, 6.3% HREE, typical of crusts elsewhere in the global ocean. An important environmental issue is high Th contents in the land-based deposits (100s of ppm); in contrast to low Th in marine deposits (mean 14 ppm CCZ; 11 ppm PCZ). Rare metals in the marine deposits would likely be recovered as byproducts of Ni, Cu, and Co mining, with the possible exception of Te.

Thermodynamic Stability of Transition Metal Substituted LiMn 2-xMxO 4 (M=Cr, Fe, Co, and Ni) Spinels

NASA Astrophysics Data System (ADS)

Lai, Chenying

The formation enthalpies from binary oxides of LiMn2O 4, LiMn2-xCrxO4 (x = 0.25, 0.5, 0.75 and 1), LiMn2-xFexO4 (x = 0.25 and 0.5), LiMn2-xCoxO4 (x = 0.25, 0.5, and 0.75) and LiMn1.75Ni 0.25O4 at 25 °C have been measured by high-temperature oxide-melt-solution calorimetry and were found to be strongly exothermic. Increasing Cr, Co and Ni content leads to more thermodynamically stable spinels, but increasing Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO 4 (M = Cr, Fe and Co) become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4 - LiMnMO 4 solid solutions. These data confirm that transition metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Rational Design of Na(Li1/3 Mn2/3 )O2 Operated by Anionic Redox Reactions for Advanced Sodium-Ion Batteries.

PubMed

Kim, Duho; Cho, Maenghyo; Cho, Kyeongjae

2017-09-01

In an effort to develop high-energy-density cathodes for sodium-ion batteries (SIBs), low-cost, high capacity Na(Li 1/3 Mn 2/3 )O 2 is discovered, which utilizes the labile O 2p-electron for charge compensation during the intercalation process, inspired by Li 2 MnO 3 redox reactions. Na(Li 1/3 Mn 2/3 )O 2 is systematically designed by first-principles calculations considering the Li/Na mixing enthalpy based on the site preference of Na in the Li sites of Li 2 MnO 3 . Using the anionic redox reaction (O 2- /O - ), this Mn-oxide is predicted to show high redox potentials (≈4.2 V vs Na/Na + ) with high charge capacity (190 mAh g -1 ). Predicted cathode performance is validated by experimental synthesis, characterization, and cyclic performance studies. Through a fundamental understanding of the redox reaction mechanism in Li 2 MnO 3 , Na(Li 1/3 Mn 2/3 )O 2 is designed as an example of a new class of promising cathode materials, Na(Li 1/3 M 2/3 )O 2 (M: transition metals featuring stabilized M 4+ ), for further advances in SIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The phase structure and electrochemical performance of xLi2MnO3·(1 - x)LiNi1/3Co1/3Mn1/3O2 during the synthesis and charge-discharge process

NASA Astrophysics Data System (ADS)

Yuan, Ting; Liu, HongQuan; Gu, YiJie; Cui, HongZhi; Wang, YanMin

2016-09-01

The lithium-rich layered xLi2MnO3·(1 - x)LiNi1/3Co1/3Mn1/3O2 materials were simply prepared by the molten-salt method. The effects of reaction temperature and x value on the phase structure and electrochemistry were systemically studied by X-ray diffraction, galvanostatical charge/discharge and electrochemical impedance spectroscopy (EIS). It has been found that the obtained phase is sensitive to the reaction temperature and composition. A layered rock-salt form with hexagonal α-NaFeO2-type structure occurs at 700 °C, while a spinel LiMn2O4 becomes the main phase at 800 °C. Besides, a spinel Li4Mn5O12 component can be found in the lithium-rich layered material when x value decreases to 0.4. The 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 material can deliver a high initial discharge capacity of 218 mAhg-1 under 20 mAg-1 current rate, then increase to the maximum 241 mAhg-1 after 4 cycles. It is confirmed by different cycle d Q/d V profile change that the layer rock-salt transforms into the two phases with the layer rock-salt phase and the spinel phase step by step. According to the EIS analysis, the 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 sample with the better electrochemical performance shows the smaller charge transfer resistance and Warburg impedance associated with Li-ion diffusion through cathode, which is attributed to contribution from a fast 3D Li-ion diffusion channel of appropriate Li4Mn5O12 phase.

Metals in Racomitrium lanuginosum from Arctic (SW Spitsbergen, Svalbard archipelago) and alpine (Karkonosze, SW Poland) tundra.

PubMed

Wojtuń, Bronisław; Samecka-Cymerman, Aleksandra; Kolon, Krzysztof; Kempers, Alexander J

2018-05-01

Arctic-alpine tundra habitats are very vulnerable to the input of relatively small amounts of xenobiotics, and thus their level in such areas must be carefully controlled. Therefore, we collected the terrestrial widespread moss Racomitrium lanuginosum (Hedw.) Brid. in Spitsbergen in the Arctic moss lichen tundra and, for comparison, in the Arctic-alpine tundra in the Karkonosze (SW Poland). Concentrations of the elements Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Na, Ni, Pb, V, and Zn in this species and in the parent rock material were measured. We tested the following hypothesis: R. lanuginosum from Spitsbergen contains lower metal levels than the species from the Karkonosze collected at altitudes influenced by long-range transport from former Black Triangle industry. Principal component and classification analysis (PCCA) ordination revealed that mosses of Spitsbergen were distinguished by a significantly higher Na concentration of marine spray origin and mosses of Karkonosze were distinguished by significantly higher concentrations of Cd, Cr, Cu, Fe, Hg, Li, Mn, Pb, V, and Zn probably from long-range atmospheric transport. The influence of the polar station with a waste incinerator resulted in significantly higher Co, Li, and Ni concentrations in neighbouring mosses in comparison with this species from other sites. This investigation contributes to the use of R. lanuginosum as a bioindicator for metal contamination in Arctic and alpine tundra regions characterised by severe climate habitats with a restricted number of species. This moss enables the control of pollution usually brought solely by long-range atmospheric transport in high mountains as well as in Arctic areas.

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

PubMed

Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

2015-02-07

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O(2-) ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O(2-) (plateau) while Fe seems to retain its 3+ state.

A Search for the Optimum Lithium Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries

PubMed Central

Ates, Mehmet Nurullah; Mukerjee, Sanjeev; Abraham, K. M.

2015-01-01

We report the results of a comprehensive study of the relationship between electrochemical performance in Li cells and chemical composition of a series of Li rich layered metal oxides of the general formula xLi2MnO3 · (1-x)LiMn0.33Ni0.33Co0.33O2 in which x = 0,1, 0.2, 0,3, 0.5 or 0.7, synthesized using the same method. In order to identify the cathode material having the optimum Li cell performance we first varied the ratio between Li2MnO3 and LiMO2 segments of the composite oxides while maintaining the same metal ratio residing within their LiMO2 portions. The materials with the overall composition 0.5Li2MnO3 · 0.5LiMO2 containing 0.5 mole of Li2MnO3 per mole of the composite metal oxide were found to be the optimum in terms of electrochemical performance. The electrochemical properties of these materials were further tuned by changing the relative amounts of Mn, Ni and Co in the LiMO2 segment to produce xLi2MnO3 · (1-x)LiMn0.50Ni0.35Co0.15O2 with enhanced capacities and rate capabilities. The rate capability of the lithium rich compound in which x = 0.3 was further increased by preparing electrodes with about 2 weight-percent multiwall carbon nanotube in the electrode. Lithium cells prepared with such electrodes were cycled at the 4C rate with little fade in capacity for over one hundred cycles. PMID:26478598

Investigation into the stress corrosion cracking properties of AA2099, an aluminum-lithium-copper alloy

NASA Astrophysics Data System (ADS)

Padgett, Barbara Nicole

Recently developed Al-Li-Cu alloys show great potential for implementation in the aerospace industry because of the attractive mix of good mechanical properties and low density. AA2099 is an Al-Li-Cu alloy with the following composition Al-2.69wt%Cu-1.8wt%Li-0.6wt%Zn-0.3wt%Mg-0.3wt%Mn-0.08wt%Zr. The environmental assisted cracking and localized corrosion behavior of the AA2099 was investigated in this thesis. The consequences of uncontrolled grain boundary precipitation via friction stir welding on the stress corrosion cracking (SCC) behavior of AA2099 was investigated first. Using constant extension rate testing, intergranular corrosion immersion experiments, and potentiodynamic scans, the heat-affected zone on the trailing edge of the weld (HTS) was determined to be most susceptible of the weld zones. The observed SCC behavior for the HTS was linked to the dissolution of an active phase (Al2CuLi, T1) populating the grain boundary. It should be stated that the SCC properties of AA2099 in the as-received condition were determined to be good. Focus was then given to the electrochemical behavior of precipitate phases that may occupy grain and sub-grain boundaries in AA2099. The grain boundary micro-chemistry and micro-electrochemistry have been alluded to within the literature as having significant influence on the SCC behavior of Al-Li-Cu alloys. Major precipitates found in this alloy system are T1 (Al 2CuLi), T2 (Al7.5Cu4Li), T B (Al6CuLi3), and theta (Al2 Cu). These phases were produced in bulk form so that the electrochemical nature of each phase could be characterized. It was determined T1 was most active electrochemically and theta was least. When present on grain boundaries in the alloy, electrochemical behavior of the individual precipitates aligned with the observed corrosion behavior of the alloy (e.g. TB was accompanied by general pitting corrosion and T 1 was accompanied by intergranular corrosion attack). In addition to the electrochemical behavior of the above-mentioned intermetallics, the phenomenon of Zn substituting for Cu in T1 was also studied. It was determined that for Zn substitutions up to 8.4wt%, improved corrosion behavior of T 1 would occur by dealloying of Zn and Li. Lastly, isothermal aging treatments at 160°C and 190°C were conducted to vary the grain boundary structures in a systematic way. The SCC behaviors for the under-aged, peak-aged, and over-aged condition were studied using CERT and alternate immersion testing at each temperature. The severely under-aged condition (≤ 9 hours) at 160°C proved to have poorest SCC resistance. The over-aged condition at 160°C (≥ 24 hours) also had degraded SCC resistance. In contrast the 190°C isothermal aging condition produced better SCC resistance than 160°C isothermal aging temperature for all conditions. The differences in behavior were linked to the species populating the grain boundaries in each isothermal aging condition (T2 at 190°C and T1 at 160°C).

Synthesis and characterization of lithium aluminum-doped spinel (LiAl xMn 2- xO 4) for lithium secondary battery

NASA Astrophysics Data System (ADS)

Lee, Yun-Sung; Kumada, Naoki; Yoshio, Masaki

LiAl xMn 2- xO 4 has been synthesized using various aluminum starting materials, such as Al(NO 3) 3, Al(OH) 3, AlF 3 and Al 2O 3 at 600-800°C for 20 h in air or oxygen atmosphere. A melt-impregnation method was used to synthesize Al-doped spinel with good battery performance in this research. The Al-doped content and the intensity ratio of (3 1 1)/(4 0 0) peaks can be important parameters in synthesizing Al-doped spinel which satisfies the requirements of high discharge capacity and good cycleability at the same time. The decrease in Mn 3+ ion by Al substitution induces a high average oxidation state of Mn ion in the LiAl xMn 2- xO 4 material. The electrochemical behavior of all samples was studied in Li/LiPF 6-EC/DMC (1:2 by volume)/LiAl xMn 2- xO 4 cells. Especially, the initial and last discharge capacity of LiAl 0.09Mn 1.97O 4 using LiOH, Mn 3O 4 and Al(OH) 3 complex were 128.7 and 115.5 mAh/g after 100 cycles. The Al substitution in LiMn 2O 4 was an excellent method of enhancing the cycleability of stoichiometric spinel during electrochemical cycling.

Microwave synthesis and electrochemical properties of lithium manganese borate as cathode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Ma, Ting; Muslim, Arzugul; Su, Zhi

2015-05-01

Nano structured LiMnBO3/C cathode materials are synthesized by a fast microwave solid-state reaction method using MnCO3, Li2CO3, H3BO3 and glucose as starting materials for the first time. The crystal structure, morphology and electrochemical properties of LiMnBO3/C composites are characterized by X-ray diffraction (XRD), raman spectroscopy (Ramon), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge-discharge tests. The result shows that not only monoclinic LiMnBO3/C but also hexagonal LiMnBO3/C cathode materials can be successfully synthesized by microwave solid-state method with power of 240 W in different time. Compared with h-LiMnBO3/C and mixed phase LiMnBO3/C, m-LiMnBO3/C displays lower charge-transfer resistance and the Warburg impedance, so it reveals a higher first discharge capacity of 156.3 mAh g-1 at 0.05 C within 1.8V-4.6 V, The value increases up to 173.2 mAh g-1 caused by the activation process. Even after 50 cycles, the discharge capacity of m-LiMnBO3/C still remains at 148.2 mAh g-1.

Enhanced electrochemical properties of F-doped Li2MnSiO4/C for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Chao; Xu, Youlong; Sun, Xiaofei; Zhang, Baofeng; Chen, Yanjun; He, Shengnan

2018-02-01

The Li2MnSiO4 as a novel cathode material for lithium ion batteries, performs high specific capacity, high thermal stability, low cost and etc. However, it suffers from relatively low electronic conductivity and lithium ion diffusion rate. Herein, we successfully introduce fluorine to Li2MnSiO4 (Li2MnSiO4-xFx, x = 0.00, 0.01, 0.03 and 0.05) to overcome these obstacles. The results show that F doping not only enlarges the lattice parameters but also decreases the particle size, synergistically improving the lithium ion diffusion of Li2MnSiO4. Moreover, F doping increase electronic conductivity of Li2MnSiO4/C by inhibiting the formation of C-O bonds in the carbon layers. Meanwhile, F doping improves the crystallinity and stabilizes the crystal structure of Li2MnSiO4. Finally, the Li2MnSiO3.97F0.03/C with the best electrochemical performances delivers the initial specific discharge capacity of 279 mA h g-1 at 25mA g-1 current density from 1.5 V to 4.8 V. Also, it maintains a higher capacity (201 mA h g-1) than F-free Li2MnSiO4 (145 mA h g-1) after 50 cycles.

Role of Cr 3+ /Cr 6+ redox in chromium-substituted Li 2 MnO 3 ·LiNi 1/2 Mn 1/2 O 2 layered composite cathodes: electrochemistry and voltage fade

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Eungje; Park, Joong Sun; Wu, Tianpin

2015-01-01

The substitution of chromium into the composite Li 2MnO 3·LiNi 1/2Mn 1/2O 2cathode dramatically affects the initial electrochemical activation process; however the voltage fade process during cycling persists.

LiMn2O4–yBryNanoparticles Synthesized by a Room Temperature Solid-State Coordination Method

PubMed Central

2009-01-01

LiMn2O4–yBrynanoparticles were synthesized successfully for the first time by a room temperature solid-state coordination method. X-ray diffractometry patterns indicated that the LiMn2O4–yBrypowders were well-crystallized pure spinel phase. Transmission electron microscopy images showed that the LiMn2O4–yBrypowders consisted of small and uniform nanosized particles. Synthesis conditions such as the calcination temperature and the content of Br−were investigated to optimize the ideal condition for preparing LiMn2O4–yBrywith the best electrochemical performances. The optimized synthesis condition was found in this work; the calcination temperature is 800 °C and the content of Br−is 0.05. The initial discharge capacity of LiMn2O3.95Br0.05obtained from the optimized synthesis condition was 134 mAh/g, which is far higher than that of pure LiMn2O4, indicating introduction of Br−in LiMn2O4is quite effective in improving the initial discharge capacity. PMID:20628635

A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

PubMed

Wang, Jiali; Wu, Hailong; Cui, Yanhua; Liu, Shengzhou; Tian, Xiaoqing; Cui, Yixiu; Liu, Xiaojiang; Yang, Yin

2018-02-14

Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li 2 MnO 3 delivers high capacity over 200 mAh g -1 but suffers from poor structural stability and electronic conductivity. Replacing Mn 4+ ions by relatively larger Sn 4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li 2 MnO 3 material. However, large difference in ionic radii of Mn 4+ and Sn 4+ ions leads to phase separation of Li 2 MnO 3 and Li 2 SnO 3 during high-temperature synthesis. To prepare solid-solution phase of Li 2 MnO 3 -Li 2 SnO 3 , a buffer agent of Ru 4+ , whose ionic radius is in between that of Mn 4+ and Sn 4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li + /e - transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn 4+ ions with larger sizes could partially block the migration of Mn 4+ and Ru 4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

Investigating the stability of cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Yiqing

Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from XAS and XPS analysis. Safety of batteries not only depends on the stability of the active materials, but also the interactions between the active materials and electrolyte. Thus we study the stability between the cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the influence of n--butyllithium (n--BuLi) treatments on the electrochemical performance of the aerogel. In addition to fully reversible V reduction and oxidation due to the intercalation reaction, we observe the formation of LiOH species that are only partially reversible. This is attributed to reaction with the interlayer water and is considered responsible for the gradual capacity fade. The n--BuLi treated aerogels display a higher capacity than those without and our XPS analysis reveals an additional reversible formation of Li2O.

Transition metal redox and Mn disproportional reaction in LiMn0.5Fe0.5PO4 electrodes cycled with aqueous electrolyte

NASA Astrophysics Data System (ADS)

Zhuo, Zengqing; Hu, Jiangtao; Duan, Yandong; Yang, Wanli; Pan, Feng

2016-07-01

We performed soft x-ray absorption spectroscopy (sXAS) and a quantitative analysis of the transition metal redox in the LiMn0.5Fe0.5PO4 electrodes upon electrochemical cycling. In order to circumvent the complication of the surface reactions with organic electrolyte at high potential, the LiMn0.5Fe0.5PO4 electrodes are cycled with aqueous electrolyte. The analysis of the transitional metal L-edge spectra allows a quantitative determination of the redox evolution of Mn and Fe during the electrochemical cycling. The sXAS analysis reveals the evolving Mn oxidation states in LiMn0.5Fe0.5PO4. We found that electrochemically inactive Mn2+ is formed on the electrode surface during cycling. Additionally, the signal indicates about 20% concentration of Mn4+ at the charged state, providing a strong experimental evidence of the disproportional reaction of Mn3+ to Mn2+ and Mn4+ on the surface of the charged LiMn0.5Fe0.5PO4 electrodes.

First-principles study of lithium ion migration in lithium transition metal oxides with spinel structure.

PubMed

Nakayama, Masanobu; Kaneko, Mayumi; Wakihara, Masataka

2012-10-28

The migration of lithium (Li) ions in electrode materials is an important factor affecting the rate performance of rechargeable Li ion batteries. We have examined Li migration in spinels LiMn(2)O(4), LiCo(2)O(4), and LiCo(1/16)Mn(15/16)O(4) by means of first-principles calculations based on density functional theory (DFT). The results showed that the trajectory of the Li jump was straight between the two adjacent Li ions for all of the three spinel compounds. However, there were significant differences in the energy profiles and the Li jump path for LiMn(2)O(4) and LiCo(2)O(4). For LiMn(2)O(4) the highest energy barrier was in the middle of the two tetrahedral sites, or in the octahedral vacancy (16c). For LiCo(2)O(4) the lowest energy was around the octahedral 16c site and the energy barrier was located at the bottleneck sites. The difference in the energy profile for LiCo(2)O(4) stemmed from the charge disproportion of Co(3.5+) to Co(3+)/Co(4+) caused by a Li vacancy forming and jumping, which was not observed for LiMn(2)O(4). Charge disproportion successfully accounted for the faster Li migration mechanism observed in LiCo(1/16)Mn(15/16)O(4). Our computational results demonstrate the importance of the effect of charge distribution on the ion jump.

Synthesis, characterization and electrochemmistry of lithium battery electrodes : xLi{sub 2}MnO{sub 3}{center_dot}(1-x)LiMn{sub 0.333}Ni{sub 0.333}Co{sub 0.333}O{sub2} (0{le}x{le}0.7).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, C. S.; Li, N.; Lefief, C.

2008-01-01

Lithium- and manganese-rich layered electrode materials, represented by the general formula xLi{sub 2}MnO{sub 3} {center_dot} (1-x)LiMO{sub 2} in which M is Mn, Ni, and Co, are of interest for both high-power and high-capacity lithium ion cells. In this paper, the synthesis, structural and electrochemical characterization of xLi{sub 2}MnO{sub 3} {center_dot} (1-x)LiMn{sub 0.333}Ni{sub 0.333}Co{sub 0.333}O{sub 2} electrodes over a wide compositional range (0 {le} x {le} 0.7) is explored. Changes that occur to the compositional, structural, and electrochemical properties of the electrodes as a function of x and the importance of using a relatively high manganese content and a high chargingmore » potential (>4.4 V) to generate high capacity (>200 mAh/g) electrodes are highlighted. Particular attention is given to the electrode composition 0.3Li{sub 2}MnO{sub 3} {center_dot} 0.7LiMn{sub 0.333}Ni{sub 0.333}Co{sub 0.333}O{sub 2} (x = 0.3) which, if completely delithiated during charge, yields Mn{sub 0.533}Ni{sub 0.233}Co{sub 0.233}O{sub 2}, in which the manganese ions are tetravalent and, when fully discharged, LiMn{sub 0.533}Ni{sub 0.233}Co{sub 0.233}O{sub 2}, in which the average manganese oxidation state (3.44) is marginally below that expected for a potentially damaging Jahn-Teller distortion (3.5). Acid treatment of 0.3Li{sub 2}MnO{sub 3} {center_dot} 0.7LiMn{sub 0.333}Ni{sub 0.333}Co{sub 0.333}O{sub 2} composite electrode structures with 0.1 M HNO{sub 3} chemically activates the Li{sub 2}MnO{sub 3} component and essentially eliminates the first cycle capacity loss but damages electrochemical behavior, consistent with earlier reports for Li{sub 2}MnO{sub 3}-stabilized electrodes. Differences between electrochemical and chemical activation of the Li{sub 2}MnO{sub 3} component are discussed. Electrochemical charge/discharge profiles and cyclic voltammogram data suggest that small spinel-like regions, generated in cycled manganese-rich electrodes, serve to stabilize the electrodes, particularly at low lithium loadings (high potentials). The study emphasizes that, for high values of x, a relatively small LiMO{sub 2} concentration stabilizes a layered Li{sub 2}MnO{sub 3} electrode to reversible lithium insertion and extraction when charged to a high potential.« less

Preparation and some properties of Cu-Li alloys containing up to 20 at. % Li

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mendelsohn, M.; Krauss, A.R.; Gruen, D.M.

1985-01-01

Lithium strongly segregates to the surface of Cu-Li alloys, thus substantially lowering the Cu sputtering yield relative to pure Cu. Use of Cu-Li limiters or divertors in tokamaks can therefore be expected to be beneficial in limiting high-Z plasma impurity influx. A large scale (100-200g) method for the preparation of Cu-Li alloys is described. Analysis reveals that on solidification from the melt stratification occurs which leads to compositional inhomogeneity. The results are discussed in the light of the Cu-Li binary phase diagram and rationalized on the basis of large density differences between Cu and Cu-Li solid solutions. It is concludedmore » that obtaining homogeneous Cu-Li solid solutions is a nontrivial task.« less

Trace Elements in Manganese Minerals as Potential Biosignatures on Mars

NASA Astrophysics Data System (ADS)

Lanza, N.; Clegg, S. M.; Cousin, A.; Forni, O.; Kirk, M. F.; Lamm, S. N.; Ollila, A.; Wiens, R. C.

2017-12-01

Observations from the Curiosity rover in Gale crater, Mars have shown the presence of high abundances of manganese (>3 wt% MnO) within sedimentary rocks throughout the traverse. Such high Mn abundances point to the past presence of abundant liquid water and strongly oxidizing conditions. On Earth, these types of environments are almost always habitable and are frequently inhabited by microbes. Given its close association with life and habitable environments on Earth, manganese has long been considered a potential biosignature for Mars. However, high concentrations of martian Mn have only recently been observed. In addition to the observations in Gale crater, high abundances of Mn have also been observed in Endeavor crater by the Opportunity rover and in the paired martian meteorites NWA 7034 and 7533 (`Black Beauty'), suggesting that Mn deposits may be more widespread on Mars than previously thought. The goal of this work is to determine whether there are unique signatures from rover payload instruments that can distinguish Mn-rich deposits as biogenic in origin (i.e., produced by life) from abiogenic Mn deposits. Importantly, Mn-oxides are known to scavenge trace metals from water because of their surface charge properties. We hypothesize that the presence and abundance of specific trace elements are the critical, distinguishing evidence for identifying the biogenic origin of Mn-bearing materials. A suite of natural rocks containing Mn-rich minerals with a range of Mn redox states was selected for analysis with laser-induced breakdown spectroscopy (LIBS). Samples with a biogenic origin had mixed valence redox states between Mn3+ and Mn4+ as inferred by mineralogy. Trace elements Ba, Li, Sr, and Rb were quantified and the presence or absence of Zn and Cu was ascertained by examining key LIBS peaks. Results show that samples with a known microbial origin had moderate Mn abundances >30 wt% MnO and higher Li and Ba. These results suggest that high Mn abundance alone is not sufficient evidence of a biosignatures. However, the presence of trace elements may help to infer the redox state of Mn, which may in turn point to samples that are more likely to have a biogenic origin.

Effect of Ni and Ti substitutions on Li1.05Mn2O4-δ electrical conductivities at high temperature

NASA Astrophysics Data System (ADS)

Abe, Satoko; Iwasaki, Shoko; Shimonishi, Yuta; Komine, Shigeki; Munakata, Fumio

2016-10-01

Samples of Li1.05Mn2O4-δ, Li1.05Mn1.5Ni0.5O4-δ, and Li1.05Mn1.0Ni0.5Ti0.5O4-δ were prepared by a solid-state reaction technique and ultimately refined to a space group Fd-3m of spinel structure by the Rietveld method using synchrotron powder X-ray diffraction data. Comparison of lattice constants suggested that Ni-substitution increased the covalency in the bonding of MO6 (M: metal ion at 16d site) octahedrals, but Ni/Ti co-substitution decreased the covalency of M-O bonds and introduced structural distortion. Electrical conductivity measurements by a four-probe method resulted in the determination that electrical conduction (within all samples) exhibits a nonadiabatic hopping process at high temperatures. The activation energies of Li1.05Mn2O4-δ and Li1.05Mn1.5Ni0.5O4-δ were found to be of similar values. The Ni/Ti co-substituted sample of Li1.05Mn1.0Ni0.5Ti0.5O4-δ, on the other hand, showed the highest activation energy among all the measured samples. Substitution reduced the electrical conductivity relative to Li1.05Mn2O4-δ; furthermore, both the substituted samples (Li1.05Mn1.5Ni0.5O4-δ and Li1.05Mn1.0Ni0.5Ti0.5O4-δ) were found to exhibit functional independence from oxygen partial pressure (PO2).

Band diagram and rate analysis of thin film spinel LiMn 2O 4 formed by electrochemical conversion of ALD-grown MnO

DOE PAGES

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; ...

2016-09-22

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

A stepwise recovery of metals from hybrid cathodes of spent Li-ion batteries with leaching-flotation-precipitation process

NASA Astrophysics Data System (ADS)

Huang, Yanfang; Han, Guihong; Liu, Jiongtian; Chai, Wencui; Wang, Wenjuan; Yang, Shuzhen; Su, Shengpeng

2016-09-01

The recovering of valuable metals in spent lithium-ion battery cathodes brings about economic and environmental benefits. A stepwise leaching-flotation-precipitation process is adopted to separate and recover Li/Fe/Mn from the mixed types of cathode materials (hybrid wastes of LiFePO4 and LiMn2O4). The optimal operating conditions for the stepwise recovery process are determined and analyzed by factorial design, thermodynamics calculation, XRD and SEM characterization in this study. First, Li/Fe/Mn ions are released from the cathode using HCl assisted with H2O2 in the acid leaching step. The leachability of metals follows the series Li > Fe > Mn in the acidic environment. Then Fe3+ ions are selectively floated and recovered as FeCl3 from the leachate in the flotation step. Finally, Mn2+/Mn3+ and Li+ ions are sequentially precipitated and separated as MnO2/Mn2O3 and Li3PO4 using saturated KMnO4 solution and hot saturated Na3PO4 solution, respectively. Under the optimized and advisable conditions, the total recovery of Li, Fe and Mn is respectively 80.93 ± 0.16%, 85.40 ± 0.12% and 81.02 ± 0.08%. The purity for lithium, ferrum and manganese compounds is respectively 99.32 ± 0.07%, 97.91 ± 0.05% and 98.73 ± 0.05%. This stepwise process could provide an alternative way for the effective separation and recovery of metal values from spent Li-ion battery cathodes in industry.

Electron diffraction and high-resolution electron microscopy studies on layered Li{sub 2−δ}(Mn{sub 1−x}Co{sub x}){sub 1+δ}O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujii, Hiroki, E-mail: fujii.hiroki@nims.go.jp; Ozawa, Kiyoshi; Mochiku, Takashi

2013-07-15

The structure of Li{sub 2}MnO{sub 3}–LiCoO{sub 2} solid solutions or Li{sub 2−δ}(Mn{sub 1−x}Co{sub x}){sub 1+δ}O{sub 3} (LMCO) which are promising lithium-battery cathodes was studied by high-resolution electron microscopy (HREM). X-ray diffraction (XRD) analyses indicate that Li{sub 1.6}Mn{sub 0.2}Co{sub 1.2}O{sub 3} and Li{sub 1.7}Mn{sub 0.4}Co{sub 0.9}O{sub 3} take a rhombohedral (R3-bar m space group) structure, whereas Li{sub 1.85}Mn{sub 0.7}Co{sub 0.45}O{sub 3} and Li{sub 1.95}Mn{sub 0.9}Co{sub 0.15}O{sub 3} take a monoclinic (C2/m) superstructure. HREM studies on those samples reveal that all of the observed crystallites in sample Li{sub 1.95}Mn{sub 0.9}Co{sub 0.15}O{sub 3} contain sharp stripe structures due to the planar defects alongmore » the c{sub h}-axis (stacking direction of the hexagonal close-packed planes) of parent rhombohedral R3-bar m cell. Such stripe structures become faint with increasing x, Co content. The origin of the planar defects is mainly attributed not to the different structures but to the different local orientations of the monoclinic LMCO. Local disordering of Li and (Mn,Co) in (Li,Mn,Co) planes is developed with increasing x and the structures are transformed from C2/m to R3-bar m. The alternative (Li,Mn,Co)-plane stacking structure, trigonal P3{sub 1}12 LMCO, was occasionally observed. However, only P3{sub 1}12 LMCO platelets with a thickness of a single unit cell were detected. - Graphical abstract: An HREM image for Li{sub 1.95}(Mn{sub 0.9}Co{sub 0.15})O{sub 3} and schematic drawings of C2/m and P3{sub 1}12 Li{sub 2}MnO{sub 3} projected along the various zone axes. Each projected unit cell is indicated by rectangles and parallelograms . - Highlights: • Li{sub 2−δ}(Mn{sub 1−x}Co{sub x}){sub 1+δ}O{sub 3} was studied by high-resolution electron microscopy (HREM). • HREM studies revealed a large amount of planar defects in C2/m Li{sub 1.95}Mn{sub 0.9}Co{sub 0.15}O{sub 3}. • The origin of the defects is the different local orientations of the C2/m platelets. • P3{sub 1}12 platelets with only single unit cell sequence were detected.« less

Effect of AlP coating on electrochemical properties of LiMn{sub 2}O{sub 4} cathode material for lithium ion battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Xiaoyu; Zhang, Jianxin, E-mail: jianxin@sdu.edu.cn; Yin, Longwei

2016-02-15

Highlights: • Modified LiMn{sub 2}O{sub 4} surface with AlP successfully. • AlP coating surface modification enhances the cycling stability of LiMn{sub 2}O{sub 4} at both room temperature and 60 °C. • AlP coating surface modification improves the rate capability of LiMn{sub 2}O{sub 4}. - Abstract: AlP-modified LiMn{sub 2}O{sub 4} has been synthesized via a simple chemical deposition method followed by high-temperature heating. The X-ray diffraction patterns, SEM images and Energy Dispersive Spectrometer show the successful surface coating of LiMn{sub 2}O{sub 4} by F-43 m crystal form AlP. AlP-modified LiMn{sub 2}O{sub 4} has a high discharge capacity of 125.7 mAh g{supmore » −1} with retention of 87% at a current density of 1C between 3.3 V and 4.3 V after 100 cycles at 60 °C, while bare LiMn{sub 2}O{sub 4} has more than 28% capacity loss. At 10 rates, the coated sample delivers capacity of 100 mAh g{sup −1}, which is much higher than bare LiMn{sub 2}O{sub 4}. Based on the EIS (electrochemical impedance spectroscopy) result, AlP coating can effectively inhibit the increase of the charge transfer resistance during charging and discharging cycles.« less

Total reflection X-ray fluorescence spectrometric determination of elements in water hyacinth from the Lerma River

NASA Astrophysics Data System (ADS)

Tejeda, S.; Zarazúa, G.; Ávila-Pérez, P.; Carapia-Morales, L.; Martínez, T.

2010-06-01

The Lerma River is one of the most polluted body water in Mexico. For this reason, only the highly resistant organisms such as water hyacinth are able to reproduce in this river. The aim of this work was to evaluate the concentration of K, S, Fe, Ca, Mn, Ti, Zn, Sr, Rb, Cu, Cr, Ni, Pb and Br in roots of water hyacinth ( Eichhornia crassipes) from the Lerma River. The samples were collected from five sites in the river and analyzed in triplicate using a TXRF Spectrometer 'TX-2000 Ital Structures' with a Si(Li) detector and a resolution of 140 eV (FWHM) at Mn Kα. A Mo tube (40 kV, 30 mA) with 17.4 KeV excitation energy was used for a counting time of 500 s. Results show that the average metal concentration in the water hyacinth roots decrease in the following order: K (9698.2 µg/g) > S (7593.3 µg/g) > Fe (4406.6 µg/g) > Ca (2601.8 µg/g) > Mn (604.2 µg/g) > Ti (230.7 µg/g) > Zn (51.65 µg/g) > Sr (43.55 µg/g) > Rb (18.61 µg/g) > Cu (12.78 µg/g) > Cr (6.45 µg/g) > Ni (4.68 µg/g) > Pb (4.32 µg/g) > Br (4.31 µg/g) and the bioconcentration factors in the water hyacinth decrease in the sequence: Ti > Fe > Mn > Cu > Ni > Zn > S > Pb > Rb > K > Cr > Sr > Br > Ca. The concentrations in roots of water hyacinth reflect the high pollution level of the river.

Exceptional effect of glassy lithium fluorophosphate on Mn-rich olivine cathode material for high-performance Li ion batteries

NASA Astrophysics Data System (ADS)

Kim, Jongsoon; Kim, Hyungsub; Myung, Seung-Taek; Yoo, Jung-Keun; Lee, Seongsu

2018-01-01

Mn-rich olivine LiFe0.3Mn0.7PO4 is homogenously encapsulated by an ∼3-nm-thick conductive nanolayer composed of the glassy lithium fluorophosphate through simple non-stoichiometric synthesis using additives of small amounts of LiF and a phosphorus source. The coating of the glassy lithium fluorophosphate nanolayer is clearly verified using transmission electron microscopy and X-ray photoelectron spectroscopy. It enables significant decrease in charge transfer resistance of LiFe0.3Mn0.7PO4 and improvement of its sluggish Li diffusion. At a rate of 10C, the LiFe0.3Mn0.7PO4 encapsulated by conductive glassy lithium fluorophosphate (LiFe0.3Mn0.7PO4-GLFP) electrode delivers a capacity of ∼130 mAh g-1, which is ∼77% of its theoretical capacity (∼170 mAh g-1) and ∼1.5 times higher than that of the pristine counterpart at 10C. Furthermore, LiFe0.3Mn0.7PO4-GLFP achieves outstanding cycle stability (∼75% retention of its initial capacity over 500 cycles at 1C). The proposed olivine LiFe0.3Mn0.7PO4-GLFP battery is thus expected to be a promising candidate for large-scale energy storage applications.

Distribution of chemical elements in attic dust as reflection of their geogenic and anthropogenic sources in the vicinity of the copper mine and flotation plant.

PubMed

Balabanova, Biljana; Stafilov, Trajče; Sajn, Robert; Bačeva, Katerina

2011-08-01

The main aim of this article was to assess the atmospheric pollution with heavy metals due to copper mining Bučim near Radoviš, the Republic of Macedonia. The open pit and mine waste and flotation tailings are continually exposed to open air, which leads to winds carrying the fine particles into the atmosphere. Samples of attic dust were examined as historical archives of mine emissions, with the aim of elucidating the pathways of pollution. Dust was collected from the attics of 29 houses, built between 1920 and 1970. Nineteen elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Li, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn) were analyzed by atomic emission spectrometry with inductively coupled plasma. The obtained values of the investigated elements in attic dust samples were statistically processed using nonparametric and parametric analysis. Factor analysis revealed three factors governing the source of individual chemical elements. Two of them grouping Ca, Li, Mg, Mn, and Sr (Factor 1) and Co, Cr, and Ni (Factor 2) can be characterized as geogenic. The third factor grouping As, Cu, and Pb is anthropogenic and mirrors dust fallout from mining operation and from flotation tailings. Maps of areal deposition were prepared for this group of elements, from which correlation of these anthropogenic born elements was confirmed.

Biomonitoring of 30 trace elements in urine of children and adults by ICP-MS.

PubMed

Heitland, Peter; Köster, Helmut D

2006-03-01

The paper provides physicians and clinical chemists with statistical data (concentration ranges, geometric mean values, selected percentiles, etc.) about 30 urinary trace elements in order to determine whether people have trace element deficiencies or have been exposed to higher elemental concentrations. Morning urine samples of 72 children and 87 adults from two geographical areas of Germany were collected and the elements Li, Be, V, Cr, Mn, Ni, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Rh, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, Pt, Au, Pb, Tl, Bi and U were determined by inductively coupled plasma mass spectrometry (ICP-MS) with a new octopole based collision/reaction cell. The urine samples were analysed directly after a simple 1/5 (V/V) dilution with deionised water and nitric acid. Information on exposure conditions of all human subjects were collected by questionnaire-based interviews. The described concentration data down to the ng/l range are very useful for the formulation of reference values. For some elements either new data are described (e.g., for V, Ga, In, Bi, Rh, Mn) or differences to earlier studies were found (e.g., for Be, As). For other elements (e.g., Sb, Se, Mo, Ba, Cu, Zn, Li) our results are in good correlation with previous studies and also complemented with urinary trace element concentrations for children.

Preparation and Electrochemical Performance of Li4Mn5O12 Nanorods using β-MnO2 Nanorods as Precursor

NASA Astrophysics Data System (ADS)

Zhao, Yan; Wang, Li; Mu, Yanlin; Zhang, Chongwei; Zhu, Fan; Liu, Mengjiao; Lai, Qiongyu; Bi, Jian; Gao, Daojiang

2018-03-01

Li4Mn5O12 nanorods were successfully prepared by using β-MnO2 nanorod precursors as self-templates. The obtained Li4Mn5O12 nanorods were approximately 0.8-1.5 μm in length and 0.15 μm in width, and were employed as electrode materials and applied in supercapacitors. The results show that Li4Mn5O12 nanorods can deliver 211 F g-1 within the potential range of 0-1.4 V at a scan rate of 5 mV s-1 in 1 mol L-1 Li2SO4 solution, which presents a good electrochemical performance.

Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys

DOEpatents

Ovshinsky, Stanford R.; Fetcenko, Michael A.

1996-01-01

An electrochemical hydrogen storage material comprising: (Base Alloy).sub.a M.sub.b where, Base Alloy is an alloy of Mg and Ni in a ratio of from about 1:2 to about 2:1, preferably 1:1; M represents at least one modifier element chosen from the group consisting of Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, and Ca; b is greater than 0.5, preferably 2.5, atomic percent and less than 30 atomic percent; and a+b=100 atomic percent. Preferably, the at least one modifier is chosen from the group consisting of Co, Mn, Al, Fe, and Cu and the total mass of the at least one modifier element is less than 25 atomic percent of the final composition. Most preferably, the total mass of said at least one modifier element is less than 20 atomic percent of the final composition.

Molten salt-directed synthesis method for LiMn2O4 nanorods as a cathode material for a lithium-ion battery with superior cyclability

NASA Astrophysics Data System (ADS)

Kebede, Mesfin A.; Ozoemena, Kenneth I.

2017-02-01

A molten salt synthesis technique has been used to prepare nanorods of Mn2O3 and single-crystal LiMn2O4 nanorods cathode material with superior capacity retention. The molten salt-directed synthesis involved the use of NaCl as the eutectic melt. The as-synthesized LiMn2O4 nanorods cathode material showed superior electrochemical performance compared to the LiMn2O4 sample obtained via the solid state method. The as-synthesized LiMn2O4 nanorods maintained more than 95% of the initial discharge capacity of 107 mA h g-1 over 100 cycles at a rate of 0.1 C, whereas the LiMn2O4 sample synthesized using the solid state reaction method maintained 88% of the initial discharge capacity of 98 mA h g-1 over 100 cycles at a rate of 0.1 C. Compared to the literature, the molten salt-directed method for the preparation of high-performance LiMn2O4 is simpler and less expensive, with greater potential for industrial scale-up.

Excellent rate capability and cycling stability in Li+-conductive Li2SnO3-coated LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries.

PubMed

Mou, Jirong; Deng, Yunlong; Song, Zhicui; Zheng, Qiaoji; Lam, Kwok Ho; Lin, Dunmin

2018-05-22

High-voltage LiNi0.5Mn1.5O4 is a promising cathode candidate for lithium-ion batteries (LIBs) due to its considerable energy density and power density, but the material generally undergoes serious capacity fading caused by side reactions between the active material and organic electrolyte. In this work, Li+-conductive Li2SnO3 was coated on the surface of LiNi0.5Mn1.5O4 to protect the cathode against the attack of HF, mitigate the dissolution of Mn ions during cycling and improve the Li+ diffusion coefficient of the materials. Remarkable improvement in cycling stability and rate performance has been achieved in Li2SnO3-coated LiNi0.5Mn1.5O4. The 1.0 wt% Li2SnO3-coated LiNi0.5Mn1.5O4 cathode exhibits excellent cycling stability with a capacity retention of 88.2% after 150 cycles at 0.1 C and rate capability at high discharge rates of 5 C and 10 C, presenting discharge capacities of 119.5 and 112.2 mAh g-1, respectively. In particular, a significant improvement in cycling stability at 55 °C is obtained after the coating of 1.0 wt% Li2SnO3, giving a capacity retention of 86.8% after 150 cycles at 1 C and 55 °C. The present study provides a significant insight into the effective protection of Li-conductive coating materials for a high-voltage LiNi0.5Mn1.5O4 cathode material.

CuLi2Sn and Cu2LiSn: Characterization by single crystal XRD and structural discussion towards new anode materials for Li-ion batteries.

PubMed

Fürtauer, Siegfried; Effenberger, Herta S; Flandorfer, Hans

2014-12-01

The stannides CuLi 2 Sn (CSD-427095) and Cu 2 LiSn (CSD-427096) were synthesized by induction melting of the pure elements and annealing at 400 °C. The phases were reinvestigated by X-ray powder and single-crystal X-ray diffractometry. Within both crystal structures the ordered CuSn and Cu 2 Sn lattices form channels which host Cu and Li atoms at partly mixed occupied positions exhibiting extensive vacancies. For CuLi 2 Sn, the space group F-43m. was verified (structure type CuHg 2 Ti; a =6.295(2) Å; wR 2 ( F ²)=0.0355 for 78 unique reflections). The 4( c ) and 4( d ) positions are occupied by Cu atoms and Cu+Li atoms, respectively. For Cu 2 LiSn, the space group P 6 3 / mmc was confirmed (structure type InPt 2 Gd; a =4.3022(15) Å, c =7.618(3) Å; wR 2 ( F ²)=0.060 for 199 unique reflections). The Cu and Li atoms exhibit extensive disorder; they are distributed over the partly occupied positions 2( a ), 2( b ) and 4( e ). Both phases seem to be interesting in terms of application of Cu-Sn alloys as anode materials for Li-ion batteries.

Interpreting the structural and electrochemical complexity of 0.5Li{sub 2}MnO{sub 3}{lg_bullet}.0.5LiMO{sub 2} electrodes for lithium batteries (M=Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x}, 0{le}x{le}0.5).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, S. H.; Kempgens, P.; Greenbaum, S.

2007-01-01

The structural and electrochemical features of layered 0.5Li{sub 2}MnO{sub 3} {center_dot} 0.5LiMO{sub 2} electrodes, in which M = Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x} (0{le} x {le} 0.5), have been studied by powder X-ray diffraction, electrochemical differential-capacity measurements, {sup 7}Li magic-angle-spinning nuclear magnetic resonance, and X-ray absorption near-edge spectroscopy. Li{sub 2}MnO{sub 3}-like regions in the as-prepared samples were observed for all values of x, with transition-metal cation disorder between the LiMO{sub 2} and Li{sub 2}MnO{sub 3} components increasing with cobalt content (i.e., the value of x). The structural disorder and complexity of the electrochemical redox reactions increase when the Li{sub 2}MnO{sub 3}-likemore » regions within the electrode are activated to 4.6 V in lithium cells; interpretations of structural and electrochemical phenomena are provided.« less

Insight into the Atomic Structure of High-Voltage Spinel LiNi 0.5Mn 1.5O4 Cathode Material in the First Cycle

DOE PAGES

Huang, Xuejie; Yu, Xiqian; Lin, Mingxiang; ...

2014-12-22

Application of high-voltage spinel LiNi 0.5Mn 1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi 0.5Mn 1.5O4 cathode material. Although it is well-known that the structure of LiNi 0.5Mn 1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood.more » Here, we report detailed investigations of local atomic-level and average structure of LiNi 0.5Mn 1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi 0.5Mn 1.5O4//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi 0.5Mn 1.5O4 particles show migration of TM ions into tetrahedral Li sites to form a Mn 3O 4-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi 0.5Mn 1.5O4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi 0.5Mn 1.5O4 structure to obtain better electrochemical performance.« less

Crystal growth of the quasi-one dimensional spin-magnet LiCuVO 4

NASA Astrophysics Data System (ADS)

Prokofiev, A. V.; Wichert, D.; Assmus, W.

2000-12-01

The phase relationships in the Li-Cu-V-O and Li-Cu-V-O-Cl systems were investigated and the phase diagrams determined. Based on these diagrams single crystals of the low-dimensional spin compound LiCuVO 4 with maximal dimensions up to 12×3×3 mm 3 were grown from a solution of LiCuVO 4 in a LiVO 3 or a LiVO 3-LiCl melt. The stoichiometry of the grown crystals is discussed.

Synthesis of Spherical Al-Doping LiMn2O4 via a High-Pressure Spray-Drying Method as Cathode Materials for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Yannan; Zhang, Yingjie; Zhang, Mingyu; Xu, Mingli; Li, Xue; Yu, Xiaohua; Dong, Peng

2018-05-01

Uniform and spherical LiAl0.075Mn1.925O4 particles have been successfully synthesized by the high-pressure spray-drying method. The structures and electrochemical properties of the particles were characterized by various techniques. Benefiting from the sphere-like morphology and Al-doping, LiAl0.075Mn1.925O4 delivers a capacity retention of 81.6% after 1000 cycles at 2°C, while LiMn2O4 exhibits a capacity retention of only 32.2%. The rate capability and reversible cycling performance are also improved. Furthermore, this work significantly alleviates the dissolution of Mn in LiMn2O4 materials, and effectively improves the transfer rate of lithium ions at the electrode/electrolyte interface. The spherical LiAl0.075Mn1.925O4 prepared by a facile method shows great potential for practical application in low-cost and long-life lithium-ion batteries.

Superconducting transition temperature in the Y(1-x)M(x)Ba2Cu3O(y) system

NASA Astrophysics Data System (ADS)

Suzuki, Takeyuki; Yamazaki, Tsutomu; Sekine, Ryuuta; Koukitsu, Akinori; Seki, Hisashi

1989-04-01

Experimental results are presented for the inclusion of compositional additives, M, to the sintered high-temperature superconductor Y(1-x)M(x)Ba2Cu3O(y); M can be the oxides of Mg, Ce, Gd, Yb, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and Te, as well as Li, Na, K, Ca, Sr, and La carbonates. Temperature dependence of the electrical resistance was measured down to about 80 K. Attention is given to the influence of ionic radius and the valence of the M species.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

PubMed

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

DOE PAGES

Sun, Ho-Hyun; Manthiram, Arumugam

2017-09-13

In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni 0.9Co 0.05Mn 0.05]O 2 Cathode for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ho-Hyun; Manthiram, Arumugam

In this work, to address the growing demand for energy density, the Ni-rich layered [Ni 0.90Co 0.05Mn 0.05]O 2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni 0.6Co 0.2Mn 0.2]O 2 cathode. Li[Ni 0.90Co 0.05Mn 0.05]O 2 delivers a high discharge capacity of 227 mA h g -1 compared to a capacity of 189 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the chargemore » cutoff voltage to 4.5 V, Li[Ni 0.90Co 0.05Mn 0.05]O 2 displays a capacity of 238 mA h g -1 compared to a capacity of 208 mA h g -1 for Li[Ni 0.6Co 0.2Mn 0.2]O 2. Although Li[Ni 0.90Co 0.05Mn 0.05]O 2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO 2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni 0.90Co 0.05Mn 0.05]O 2 and Li[Ni 0.6Co 0.2Mn 0.2]O 2 reveals that the capacity fade of Li[Ni 0.90Co 0.05Mn 0.05]O 2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni 0.90Co 0.05Mn 0.05]O 2.« less

Electrochemical reaction mechanisms under various charge-discharge operating conditions for Li1.2Ni0.13Mn0.54Co0.13O2 in a lithium-ion battery

NASA Astrophysics Data System (ADS)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei; Tamura, Kazuhisa

2018-06-01

The potential in each state of charge (SOC) during charging of Li1.2Ni0.13Mn0.54Co0.13O2 is higher than that during discharging. In other words, the potential hysteresis occurs between charging and discharging. Furthermore, the potential in each SOC changes according to the charge-discharge operating conditions, indicating that the charge-discharge reaction mechanism is also affected. To clarify the effect of charge-discharge operating conditions on the electrochemical reaction, Li1.2Ni0.13Mn0.54Co0.13O2 was charged and discharged under various charge-discharge operating ranges, and open-circuit potential (OCP), crystal structure, and oxidation states of the transition metals were evaluated by electrochemical measurement, X-ray diffraction (XRD), and X-ray absorption fine structure (XAFS). These results indicate that OCP, lattice parameters, and oxidation states of the transition metals of Li1.2Ni0.13Mn0.54Co0.13O2 in each SOC are not constant. The XRD results indicate that two phases, namely, LiNi0.33Mn0.33Co0.33O2-like and Li2MnO3-like, exist in Li1.2Ni0.13Mn0.54Co0.13O2. For the LiNi0.33Mn0.33Co0.33O2-like phase, the relationship between OCP, lattice parameters, and oxidation states of the transition metals in each SOC is not affected by the charge-discharge operating conditions, indicating that extraction and insertion of lithium ions for the LiNi0.33Mn0.33Co0.33O2-like phase progresses at almost the same potential. Although the extraction and insertion of lithium ions for the Li2MnO3-like phase progresses at almost the same potential in the low-SOC region, the OCP and lattice parameter in each SOC in the high-SOC region are not constant. Therefore, the extraction of lithium ions from the Li2MnO3-like phase in the high-SOC region causes the potential hysteresis of Li1.2Ni0.13Mn0.54Co0.13O2.

Mixed Mn3+/Mn4+ in high-voltage nano-structured lithium nickel manganese oxide cathode with a P4332 structure

NASA Astrophysics Data System (ADS)

Li, Yu; Gu, Yi-Jie; Chen, Yun-Bo; Liu, Hong-Quan; Han, Yong-Qin; Wang, Hai-Feng; Zhou, Heng-Hui

In this paper, we have synthesized LiNi0.5Mn1.5O4 with P4332 space group by carbonate co-precipitation. TG/DSC, TG*, ICP-OES, a gas displacement pycnometer using He gas, XPS, and XRD refinement results show that oxygen vacancies exist in the LiNi0.5Mn1.5O4-δ with a P4332 space group. There is a mixture of Mn3+ and Mn4+ in the P4332 structured LiNi0.5Mn1.5O4-δ. Despite the large amount of Mn3+ in the spinel structure, no 4.0V plateau appears in charge-discharge curves. This result indicates that the Mn3+ in LiNi0.5Mn1.5O4-δ does not participate in electrochemical reactions during the charge-discharge process.

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes

DOE PAGES

Devaraj, Arun; Gu, Meng; Colby, Robert J.; ...

2015-08-14

The distribution and concentration of lithium in Li-ion battery cathodes at different stages of cycling is a pivotal factor in determining battery performance. Non-uniform distribution of the transition metal cations has been shown to affect cathode performance; however, the Li is notoriously challenging to characterize with typical high-spatial-resolution imaging techniques. Here, for the first time, laser–assisted atom probe tomography is applied to two advanced Li-ion battery oxide cathode materials—layered Li 1.2Ni 0.2Mn 0.6O 2 and spinel LiNi 0.5Mn 1.5O 4—to unambiguously map the three dimensional (3D) distribution of Li at sub-nanometer spatial resolution and correlate it with the distribution ofmore » the transition metal cations (M) and the oxygen. The as-fabricated layered Li 1.2Ni 0.2Mn 0.6O 2 is shown to have Li-rich Li 2MO 3 phase regions and Li-depleted Li(Ni 0.5Mn 0.5)O 2 regions while in the cycled layered Li 1.2Ni 0.2Mn 0.6O 2 an overall loss of Li and presence of Ni rich regions, Mn rich regions and Li rich regions are shown in addition to providing the first direct evidence for Li loss on cycling of layered LNMO cathodes. The spinel LiNi 0.5Mn 1.5O 4 cathode is shown to have a uniform distribution of all cations. These results were additionally validated by correlating with energy dispersive spectroscopy mapping of these nanoparticles in a scanning transmission electron microscope. Thus, we have opened the door for probing the nanoscale compositional fluctuations in crucial Li-ion battery cathode materials at an unprecedented spatial resolution of sub-nanometer scale in 3D which can provide critical information for understanding capacity decay mechanisms in these advanced cathode materials.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

The relationship between lignin peroxidase and manganese peroxidase production capacities and cultivation periods of mushrooms

PubMed Central

Xu, Jian Z; Zhang, Jun L; Hu, Kai H; Zhang, Wei G

2013-01-01

Mushrooms are able to secrete lignin peroxidase (LiP) and manganese peroxidase (MnP), and able to use the cellulose as sources of carbon. This article focuses on the relation between peroxidase-secreting capacity and cultivation period of mushrooms with non-laccase activity. Methylene blue and methyl catechol qualitative assay and spectrophotometry quantitative assay show LiP secreting unvaryingly accompanies the MnP secreting in mushroom strains. The growth rates of hyphae are detected by detecting the dry hyphal mass. We link the peroxidase activities to growth rate of mushrooms and then probe into the relationship between them. The results show that there are close relationships between LiP- and/or MnP-secretory capacities and the cultivation periods of mushrooms. The strains with high LiP and MnP activities have short cultivation periods. However, those strains have long cultivation periods because of the low levels of secreted LiP and/or MnP, even no detectable LiP and/or MnP activity. This study provides the first evidence on the imitate relation between the level of secreted LiP and MnP activities and cultivation periods of mushrooms with non-laccase activity. Our study has significantly increased the understanding of the role of LiP and MnP in the growth and development of mushrooms with non-laccase activity. PMID:22966760

The synthetic evaluation of CuO-MnOx-modified pinecone biochar for simultaneous removal formaldehyde and elemental mercury from simulated flue gas.

PubMed

Yi, Yaoyao; Li, Caiting; Zhao, Lingkui; Du, Xueyu; Gao, Lei; Chen, Jiaqiang; Zhai, Yunbo; Zeng, Guangming

2018-02-01

A series of low-cost Cu-Mn-mixed oxides supported on biochar (CuMn/HBC) synthesized by an impregnation method were applied to study the simultaneous removal of formaldehyde (HCHO) and elemental mercury (Hg 0 ) at 100-300° C from simulated flue gas. The metal loading value, Cu/Mn molar ratio, flue gas components, reaction mechanism, and interrelationship between HCHO removal and Hg 0 removal were also investigated. Results suggested that 12%CuMn/HBC showed the highest removal efficiency of HCHO and Hg 0 at 175° C corresponding to 89%and 83%, respectively. The addition of NO and SO 2 exhibited inhibitive influence on HCHO removal. For the removal of Hg 0 , NO showed slightly positive influence and SO 2 had an inhibitive effect. Meanwhile, O 2 had positive impact on the removal of HCHO and Hg 0 . The samples were characterized by SEM, XRD, BET, XPS, ICP-AES, FTIR, and H 2 -TPR. The sample characterization illustrated that CuMn/HBC possessed the high pore volume and specific surface area. The chemisorbed oxygen (O β ) and the lattice oxygen (O α ) which took part in the removal reaction largely existed in CuMn/HBC. What is more, MnO 2 and CuO (or Cu 2 O) were highly dispersed on the CuMn/HBC surface. The strong synergistic effect between Cu-Mn mixed oxides was critical to the removal reaction of HCHO and Hg 0 via the redox equilibrium of Mn 4+ + Cu + ↔ Mn 3+ + Cu 2+ .

Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

2015-10-01

Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

High-rate Li-MnO2 cells for aerospace use

NASA Technical Reports Server (NTRS)

Becker-Kaiser, R.; Ruch, J.; Harms, H.-J.; Schmoede, P.; Welsh, J. R.; Vollmers, M.-J.; Pack, H.

1992-01-01

A series of comparative studies were undertaken on representative cells as objectively as possible in order to appreciate the respective advantages of the different systems. After reviewing the first test results our attention was soon focussed on the following four lithium systems: (1) Li-SOCl2; (2) Li-SO2; (3) Li-(CF(sub x))(sub n); and (4) Li-MnO2. This resulted in the decision in 1982 to adopt the Li-MnO2 system for high-rate applications.

Tuning Li-Ion Diffusion in α-LiMn 1–x Fe x PO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn1-xFexPO4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn1-xFexPO4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. Herein, olivine-structured α-LiMn0.5Fe0.5PO4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn1-xFexPO4 nanocrystals by inducing high concentrations of Fe2+-Li+ antisite defects, which showed impressive capacitymore » improvements of approaching 162, 127, 73, and 55 mAh g-1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn1-xFexPO4, which is first reported in this work) embedded in α-LiMn0.5Fe0.5PO4. Because of the coherent orientation relationship between β- and α- phases, the β-phase embedded would impede the Li+ diffusion along the [100] and/or [001] directions that was activated by the high density of Fe2+-Li+ antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe2+-Li+ antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn1-xFexPO4 nanocrystals can be tuned by generating new Li+ tunneling. These findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE PAGES

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting; ...

2017-07-13

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Synthesis and characterization of carbon coated LiCo1/3Ni1/3Mn1/3O2 and bio-mass derived graphene like porous carbon electrodes for aqueous Li-ion hybrid supercapacitor

NASA Astrophysics Data System (ADS)

Ramkumar, B.; Yuvaraj, S.; Surendran, S.; Pandi, K.; Ramasamy, Hari Vignesh; Lee, Y. S.; Kalai Selvan, R.

2018-01-01

For the fabrication of aqueous Li-ion hybrid supercapacitor, carbon coated LiCo1/3Ni1/3Mn1/3O2 (or LiCo1/3Ni1/3Mn1/3O2@C composite) is synthesized by polymeric precursor method with subsequent thermal decomposition procedures for carbon coating. Graphene like porous carbon is obtained by chemical activation from the biomass of Agave Americana. The XRD analysis reveals that LiCo1/3Ni1/3Mn1/3O2 is having a hexagonal layered structure and activated carbon exists in both amorphous and graphitic nature. The TEM image infers that LiCo1/3Ni1/3Mn1/3O2 particles having the non-uniform shape with sub-micron size and the LiCo1/3Ni1/3Mn1/3O2 particles are embedded into amorphous carbon cloud in the composite. The activated carbon shows the specific surface area of 1219 m2 g-1. Finally, the fabricated aqueous LiCo1/3Ni1/3Mn1/3O2@C‖AC hybrid supercapacitor delivers the specific capacitance of 56 F g-1 with good capacity retention even after 5000 cycles.

Nanostructured LiMn2O4 composite as high-rate cathode for high performance aqueous Li-ion hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Chen, Lina; Zhai, Wei; Chen, Long; Li, Deping; Ma, Xiaoxin; Ai, Qing; Xu, Xiaoyan; Hou, Guangmei; Zhang, Lin; Feng, Jinkui; Si, Pengchao; Ci, Lijie

2018-07-01

Nanostructured spinel LiMn2O4 and super P composite with much enhanced electrochemical performance especially ultrahigh rate capability as the cathode for aqueous hybrid supercapacitors is synthesized by ball milling commercial LiMn2O4 particles together with super P. The as-prepared composite delivers a high capacitance of 306 F g-1 at the current density of 1 A g-1 and superb rate ability of 228.6 F g-1 at 40 A g-1 in 1 M Li2SO4 aqueous electrolyte. The capacitance of the nanostructured composite is 3.5 times higher than that of pristine LiMn2O4 even being charged and discharged 80 times faster. The excellent performances are ascribed to the nanosized LiMn2O4 well dispersed into the conductive carbon matrix. LiMn2O4 and super P composite//active carbon hybrid supercapacitor is assembled and the energy density can reach up to 21.58 Wh kg-1 at 293.16 W kg-1 and 13 Wh kg-1 at 5200 W kg-1. The hybrid device also shows an excellent cycling performance, which retains 85% of the initial capacitance after 4500 cycles. This work provides an effectively facile way to produce high performance LiMn2O4-based cathodes for hybrid suercapacitors in practical applications.

Structural and electrochemical properties of the doped spinels Li 1.05M 0.02Mn 1.98O 3.98N 0.02 (M = Ga 3+, Al 3+, or Co 3+; N = S 2- or F -) for use as cathode material in lithium batteries

NASA Astrophysics Data System (ADS)

Amaral, Fábio A.; Bocchi, Nerilso; Brocenschi, Ricardo F.; Biaggio, Sonia R.; Rocha-Filho, Romeu C.

The doped and milled spinels Li 1.05M 0.02Mn 1.98O 3.98N 0.02 (M = Ga 3+, Al 3+ or Co 3+; N = S 2- or F -) are studied aiming at obtaining an improved charge/discharge cycling performance. These spinels are prepared by a solid-state reaction among the precursors ɛ-MnO 2, LiOH, and the respective oxide/salt of the doping ions at 750 °C for 72 h and milled for 30 min. The obtained spinels are characterized by XRD, SEM, and determinations of the average manganese valence n. In the charge and discharge tests, the doped spinels present outstanding initial values of the specific discharge capacity C (117-126 mA h g -1), decreasing in the following order: C(Li 1.05Al 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Al 0.02Mn 1.98F 3.02O 3.98) > C(Li 1.05Ga 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Ga 0.02Mn 1.98F 3.02O 3.98) > C(Li 1.05Co 0.02Mn 1.98S 3.02O 3.98) > C(Li 1.05Co 0.02Mn 1.98F 3.02O 3.98). The doped spinel Li 1.05Ga 0.02Mn 1.98S 3.02O 3.98 presents an excellent electrochemical performance, with a low capacity loss even after 300 charge and discharge cycles (from 120 to 115 mA h g -1 or 4%).

The influence of temperature on a nutty-cake structural material: LiMn1-xFexPO4 composite with LiFePO4 core and carbon outer layer for lithium-ion battery

NASA Astrophysics Data System (ADS)

Huo, Zhen-Qing; Cui, Yu-Ting; Wang, Dan; Dong, Yue; Chen, Li

2014-01-01

The extremely low electronic conductivity, slow ion diffusion kinetics, and the Jahn-Teller effect of LiMnPO4 limit its electrochemical performance. In this work, a nutty-cake structural C-LiMn1-xFexPO4-LiFePO4 cathode material is synthesized by hydrothermal method and further calcined at different temperatures. The influence of calcination temperature on the electrochemical behavior is investigated by X-ray diffractometer, scanning electron microscope, field-emission high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and charge-discharge tests. And the performance of C-LiMn1-xFexPO4-LiFePO4 materials has a relationship with its crystal structure. The well-crystallized Sample-600 calcined at 600 °C shows the smallest charge transfer resistance, the largest lithium ion diffusion coefficient (DLi) and the best cycling stability. The discharge capacity of Sample-600 holds around 112 mAh g-1 after the 3rd cycle at 0.1 C rate. The performances improvement of C-LiMn1-xFexPO4-LiFePO4 material can be mainly attributed to the iron diffusion from the LiFePO4 core to the outer LiMnPO4 layer under appropriate calcination temperature.

Geochemical properties of topsoil around the coal mine and thermoelectric power plant.

PubMed

Stafilov, Trajče; Šajn, Robert; Arapčeska, Mila; Kungulovski, Ivan; Alijagić, Jasminka

2018-03-19

The results of the systematic study of the spatial distribution of trace metals in surface soil over the Bitola region, Republic of Macedonia, known for its coal mine and thermo-electrical power plant activities are reported. The investigated region (3200 km 2 ) is covered by a sparse sampling grid of 5 × 5 km, but in the urban zone and around the thermoelectric power plant the sampling grid is denser (1 × 1 km). In total, 229 soil samples from 149 locations were collected including top-soil (0-5 cm) and bottom-soil samples (20-30 cm and 0-30 cm). Inductively coupled plasma - atomic emission spectrometry (ICP-AES) was applied for the determinations of 21 elements (Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn). Based on the results of factor analyses, three geogenic associations of elements have been defined: F1 (Fe, Ni, V, Co, Cr, Mn and Li), F2 (Zn, B, Cu, Cd, Na and K) and F3 (Ca, Sr, Mg, Ba and Al). Even typical trace metals such as As, Cd, Cu, Ni, P, Pb and Zn are not isolated into anthropogenic geochemical associations by multivariate statistical methods still show some trends of local anthropogenic enrichment. The distribution maps for each analyzed element is showing the higher content of these elements in soil samples collected around the thermoelectric power plants than their average content for the soil samples collected from the whole Bitola Region. It was found that this enrichment is a result of the pollution by fly ash from coal burning which deposited near the plant having a high content of these elements.

Electrochemical performance of NCM/LFP/Al composite cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Allahyari, Ehsan; Ghorbanzadeh, Milad; Riahifar, Reza; Hadavi, S. M. M.

2018-05-01

The LiNi0.5Mn0.3Co0.2O2 (NCM) was synthesized via conventional solution combustion synthesis method. Different amounts of LiFePO4 (10, 20 and 30 wt%) were added to NCM via the ball milling technique to improve electrochemical performance including discharge capacity, cycle stability, and rate capability. The LiNi0.5Mn0.3Co0.2O2/LiFePO4 containing 20 wt% LiFePO4 was considered as the optimum composition according to the electrochemical results and SEM images. The Al powder was added to optimum LiNi0.5Mn0.3Co0.2/LiFePO4-0.2 composite through planetary ball mill to enhance the conductivity of LiNi0.5Mn0.3Co0.2O2/LiFePO4-0.2. The LiNi0.5Mn0.3Co0.2O2/LiFePO4-0.2/Al composite cathodes provide better electrochemical performance compared to pure LiNi0.5Mn0.3Co0.2O2 cathodes. The results indicate that by addition of 20 wt% of LiFePO4, the internal resistance of the electrode as well as the charge transfer resistance are reduced. Due to the strong P–O bond of the PO4 in LiFePO4, side reactions between the active electrode and electrolyte is prevented. In addition, according to weakness of the Ionic conductivity in solid electrolyte, in this paper aluminum powders added to the electrode for resolving this problem.

Investigation the electroplating behavior of self formed CuMn barrier.

PubMed

Wu, Chia-Yang; Lee, Wen-Hsi; Chang, Shih-Chieh; Wang, Ying-Lang

2013-08-01

The electrical and material properties of Copper (Cu) mixed with [0-10 atomic% manganese (Mn)] and pure Cu films deposited on silicon oxide (SiO2)/silicon (Si) are explored. Cu electroplating on self formed CuMn barrier was investigated with different Mn content. The electrochemical deposition of the Cu thin film onto the electrode using CuMn barrier was investigated. Scanning electron microscopic (SEM) micrographs of copper electroplating on CuMn films were examined, and the copper nucleation behaviors changed with the Mn content. Since the electrochemical impedance spectroscopy (EIS) is widely recognized as a powerful tool for the investigation of electrochemical behaviors, the tool was also used to verify the phenomena during plating. It was found that the charge-trasfer impedance decrease with the rise in the Mn content below 5%, but increase with the rise in the Mn content higher than 5%. The result was corresponded to the surface energy, the surface morphology, the corrosion and the oxidation of the substrate.

Facile synthesis of the Li-rich layered oxide Li1.23Ni0.09Co0.12Mn0.56O2 with superior lithium storage performance and new insights into structural transformation of the layered oxide material during charge-discharge cycle: in situ XRD characterization.

PubMed

Shen, Chong-Heng; Wang, Qin; Fu, Fang; Huang, Ling; Lin, Zhou; Shen, Shou-Yu; Su, Hang; Zheng, Xiao-Mei; Xu, Bin-Bin; Li, Jun-Tao; Sun, Shi-Gang

2014-04-23

In this work, the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 was synthesized through a facile route called aqueous solution-evaporation route that is simple and without waste water. The as-prepared Li1.23Ni0.09Co0.12Mn0.56O2 oxide was confirmed to be a layered LiMO2-Li2MnO3 solid solution through ex situ X-ray diffraction (ex situ XRD) and transmission electron microscopy (TEM). Electrochemical results showed that the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 material can deliver a discharge capacity of 250.8 mAhg(-1) in the 1st cycle at 0.1 C and capacity retention of 86.0% in 81 cycles. In situ X-ray diffraction technique (in situ XRD) and ex situ TEM were applied to study structural changes of the Li-rich oxide Li1.23Ni0.09Co0.12Mn0.56O2 material during charge-discharge cycles. The study allowed observing experimentally, for the first time, the existence of β-MnO2 phase that is appeared near 4.54 V in the first charge process, and a phase transformation of the β-MnO2 to layered Li0.9MnO2 is occurred in the initial discharge process by evidence of in situ XRD pattrens and selected area electron diffraction (SAED) patterns at different states of the initial charge and discharge process. The results illustrated also that the variation of the in situ X-ray reflections during charge-discharge cycling are clearly related to the changes of lattice parameters of the as-prepared Li-rich oxide during the charge-discharge cycles.

LiNi(0.5)Mn(1.5)O4 porous nanorods as high-rate and long-life cathodes for Li-ion batteries.

PubMed

Zhang, Xiaolong; Cheng, Fangyi; Yang, Jingang; Chen, Jun

2013-06-12

Spinel-type LiNi0.5Mn1.5O4 porous nanorods assembled with nanoparticles have been prepared and investigated as high-rate and long-life cathode materials for rechargeable lithium-ion batteries. One-dimensional porous nanostructures of LiNi0.5Mn1.5O4 with ordered P4332 phase were obtained through solid-state Li and Ni implantation of porous Mn2O3 nanorods that resulted from thermal decomposition of the chain-like MnC2O4 precursor. The fabricated LiNi0.5Mn1.5O4 delivered specific capacities of 140 and 109 mAh g(-1) at 1 and 20 C rates, respectively. At a 5 C cycling rate, a capacity retention of 91% was sustained after 500 cycles, with extremely low capacity fade (<1%) during the initial 300 cycles. The remarkable performance was attributed to the porous 1D nanostructures that can accommodate strain relaxation by slippage at the subunits wall boundaries and provide short Li-ion diffusion distance along the confined dimension.

Physics and Chemistry of Creating New Titanates with Perovskite Structure

NASA Astrophysics Data System (ADS)

Politova, E. D.; Kaleva, G. M.; Golubko, N. V.; Mosunov, A. V.; Sadovskaya, N. V.; Bel'kova, D. A.; Strebkov, D. A.; Stefanovich, S. Yu.; Kiselev, D. A.; Kislyuk, A. M.

2018-06-01

The phase formation, structural features, and dielectric, ferroelectric, and piezoelectric properties of ceramics with compositions from the region of the morphotropic phase boundary in the (Na0.5Bi0.5)TiO3-BaTiO3-Bi(Mg0.5Ti0.5)O3 system modified by different low-melting additives (Bi2O3, V2O5, KCl, NaCl-LiF, LiF, CuO, and MnO2) are studied. First-order phase transitions are detected near 700-800 and 400 K that display relaxor behavior and are indicative of the presence of polar regions in a nonpolar matrix. Prospects for improving the piezoelectric properties of the modified ceramic samples are confirmed.

High-performance spinel-rich Li1.5MnTiO4+δ ultralong nanofibers as cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

Hung Vu, Ngoc; Arunkumar, Paulraj; Bin Im, Won

2017-03-01

Recently, composite materials based on Li-Mn-Ti-O system were developed to target low cost and environmentally benign cathodes for Li-ion batteries. The spinel-layered Li1.5MnTiO4+δ bulk particles showed excellent cycle stability but poor rate performance. To address this drawback, ultralong nanofibers of a Li1.5MnTiO4+δ spinel-layered heterostructure were synthesized by electrospinning. Uniform nanofibers with diameters of about 80 nm were formed of tiny octahedral particles wrapped together into 30 μm long fibers. The Li1.5MnTiO4+δ nanofibers exhibited an improved rate capability compared to both Li1.5MnTiO4+δ nanoparticles and bulk particles. The uniform one-dimensional nanostructure of the composite cathode exhibited enhanced capacities of 235 and 170 mAh g-1 at C/5 and 1 C rates, respectively. Its unique structure provided a large effective contact area for Li+ diffusion, and low charge transfer resistance. Moreover, the layered phase contributed to its capacity in over 3 V region, which increased specific energy (726 Wh kg-1) compared to the bulk particles (534 Wh kg-1).

Insertion of lattice strains into ordered LiNi0.5Mn1.5O4 spinel by mechanical stress: A comparison of perfect versus imperfect structures as a cathode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Murakami, Takeshi; Naito, Makio

2016-07-01

The Ni-doped lithium manganese oxide, LiNi0.5Mn1.5O4, has received much attention as a cathode active material in high-energy lithium-ion batteries (LIBs). This active material has two different spinel structures depending on the ordering state of the Ni and Mn ions. The ordered LiNi0.5Mn1.5O4 spinel has an inferior cathode performance than the disordered phase because of its poor electronic conductivity. However, the ordered LiNi0.5Mn1.5O4 spinel possesses the potential advantage of avoiding dissolution of the Mn ion, which is an issue for the disordered spinel. The improvement of cathode performance is important for future applications. Here, we report a unique approach to improve the cathode performance of the ordered LiNi0.5Mn1.5O4 spinel. The mechanical treatment using an attrition-type mill successfully inserted lattice strains into the ordered LiNi0.5Mn1.5O4 spinel structure without a phase transformation to the disordered phase. The insertion of lattice strains by mechanical stresses provided an increased discharge capacity and a decreased charge transfer resistance. This limited crystal structure modification improved the cathode performance. The present work has the potential for application of the mechanically treated ordered LiNi0.5Mn1.5O4 spinel as a cathode for high-energy LIBs.

Disparities of Selected Metal Levels in the Blood and Scalp Hair of Ischemia Heart Disease Patients and Healthy Subjects.

PubMed

Ilyas, Asim; Shah, Munir H

2017-12-01

Imbalances in the concentrations of trace metals have become an increasingly recognized source of infirmity worldwide particularly in the development of ischemia heart disease (IHD). Present study is intended to analyze the concentrations of Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, Sr, and Zn in the blood and scalp hair of the patients and counterpart controls by flame atomic absorption spectrometry after wet-acid digestion. On the average, Cd, Co, Cr, Fe, K, Li, Mn, Na, and Pb revealed significantly elevated concentrations in the blood of the patients compared with the controls (p < 0.05), whereas mean levels of Ca, Cd, Fe, K, Li, Pb, and Sr in the scalp hair were significantly higher in the patients than the controls (p < 0.05). Most of the metals exhibited noticeable disparities in their concentrations based on gender, abode, dietary/smoking habits, and occupations of both donor groups. The correlation study and multivariate statistical analyses revealed some significantly divergent associations and apportionment of the metals in both donor groups. Overall, comparative variations of the metal contents in blood/scalp hair of the patients were significantly different than the controls; thus, evaluation of trace metals status may be indicative of pathological disorders, such as IHD.

The relationship between lignin peroxidase and manganese peroxidase production capacities and cultivation periods of mushrooms.

PubMed

Xu, Jian Z; Zhang, Jun L; Hu, Kai H; Zhang, Wei G

2013-05-01

Mushrooms are able to secrete lignin peroxidase (LiP) and manganese peroxidase (MnP), and able to use the cellulose as sources of carbon. This article focuses on the relation between peroxidase-secreting capacity and cultivation period of mushrooms with non-laccase activity. Methylene blue and methyl catechol qualitative assay and spectrophotometry quantitative assay show LiP secreting unvaryingly accompanies the MnP secreting in mushroom strains. The growth rates of hyphae are detected by detecting the dry hyphal mass. We link the peroxidase activities to growth rate of mushrooms and then probe into the relationship between them. The results show that there are close relationships between LiP- and/or MnP-secretory capacities and the cultivation periods of mushrooms. The strains with high LiP and MnP activities have short cultivation periods. However, those strains have long cultivation periods because of the low levels of secreted LiP and/or MnP, even no detectable LiP and/or MnP activity. This study provides the first evidence on the imitate relation between the level of secreted LiP and MnP activities and cultivation periods of mushrooms with non-laccase activity. Our study has significantly increased the understanding of the role of LiP and MnP in the growth and development of mushrooms with non-laccase activity. © 2012 The Authors. Microbial Biotechnology © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Lithium ion insertion and extraction reactions with Hollandite-type manganese dioxide free from any stabilizing cations in its tunnel cavity

NASA Astrophysics Data System (ADS)

Kijima, Norihito; Takahashi, Yasuhiko; Akimoto, Junji; Awaka, Junji

2005-09-01

Lithium ion insertion and extraction reactions with a hollandite-type α-MnO 2 specimen free from any stabilizing cations in its tunnel cavity were investigated, and the crystal structure of a Li+-inserted α-MnO 2 specimen was analyzed by Rietveld refinement and whole-pattern fitting based on the maximum-entropy method (MEM). The pH titration curve of the α-MnO 2 specimen displayed a monobasic acid behavior toward Li+, and an ion-exchange capacity of 3.25 meq/g was achieved at pH>11. The Li/Mn molar ratio of the Li+-inserted α-MnO 2 specimen showed that about two Li+ ions can be chemically inserted into one unit cell of the hollandite-type structure. As the amount of Li content was increased, the lattice parameter a increased while c hardly changed. On the other hand, the mean oxidation number of Mn decreased slightly regardless of Li content whenever ions were exchanged. The Li+-inserted α-MnO 2 specimen reduced topotactically in one phase when it was used as an active cathode material in a liquid organic electrolyte (1:1 EC:DMC, 1 mol/dm 3 LiPF 6) lithium cell. An initial discharge with a capacity of approximately 230 mAh/g was achieved, and the reaction was reversible, whereas the capacity fell steadily upon cycling. About six Li+ ions could be electrochemically inserted into one unit cell of the hollandite-type structure. By contrast, the parent α-MnO 2 specimen showed a poor discharge property although no cationic residues or residual H 2O molecules remained in the tunnel space. Rietveld refinement from X-ray powder diffraction data for a Li+-inserted specimen of (Li 2O) 0.12MnO 2 showed it to have the hollandite-type structure (tetragonal; space group I4/m; a=9.993(11) and c=2.853(3) Å; Z=8; Rwp=6.12%, Rp=4.51%, RB=1.41%, and RF=0.79%; S=1.69). The electron-density distribution images in (Li 2O) 0.12MnO 2 showed that Li 2O molecules almost fill the tunnel space. These findings suggest that the presence of stabilizing atoms or molecules within the tunnel of a hollandite-type structure is necessary to facilitate the diffusion of Li+ ions during cycling.

Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

DOE PAGES

Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; ...

2014-07-09

The role of Cu-ion doping in α-MnO 2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO 2 nanowires (Cu-α-MnO 2) were prepared with varying amounts of Cu 2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO 2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO 2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn 3+ content for the Cu-α-MnO 2 nanowires. The Mn 3+/Mn 4+ couple is themediator for the rate-limiting redoxmore » driven O 2 -/OH - exchange. It is proposed that O 2 adsorbs viaan axial site (the e g orbital on the Mn 3+ d 4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O 2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn 3+ character of the oxide.« less

High-energy X-ray powder diffraction and atomic-pair distribution-function studies of charged/discharged structures in carbon-hybridized Li2MnSiO4 nanoparticles as a cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Moriya, Maki; Miyahara, Masahiko; Hokazono, Mana; Sasaki, Hirokazu; Nemoto, Atsushi; Katayama, Shingo; Akimoto, Yuji; Hirano, Shin-ichi; Ren, Yang

2014-10-01

The stable cycling performance with a high discharge capacity of ∼190 mAh g-1 in a carbon-hybridized Li2MnSiO4 nanostructured powder has prompted an experimental investigation of the charged/discharged structures using synchrotron-based and laboratory-based X-rays and atomic-pair distribution-function (PDF) analyses. A novel method of in-situ spray pyrolysis of a precursor solution with glucose as a carbon source enabled the successful synthesis of the carbon-hybridized Li2MnSiO4 nanoparticles. The XRD patters of the discharged (lithiated) samples exhibit a long-range ordered structure characteristic of the (β) Li2MnSiO4 crystalline phase (space group Pmn21) which dissipates in the charged (delithiated) samples. However, upon discharging the long-range ordered structure recovers in each cycle. The disordered structure, according to the PDF analysis, is mainly due to local distortions of the MnO4 tetrahedra which show a mean Mn-O nearest neighbor distance shorter than that of the long-range ordered phase. These results corroborate the notion of the smaller Mn3+/Mn4+ ionic radii in the Li extracted phase versus the larger Mn2+ ionic radius in Li inserted phase. Thus Li extraction/insertion drives the fluctuation between the disordered and the long-range ordered structures.

Electrochemical properties and structures of the mixed-valence lithium cuprates Li 3Cu 2O 4 and Li 2NaCu 2O 4

NASA Astrophysics Data System (ADS)

Raekelboom, E. A.; Hector, A. L.; Weller, M. T.; Owen, J. R.

The electrochemical performances of Li 3Cu 2O 4 and Li 2NaCu 2O 4 as cathode materials in lithium coin type batteries have been studied. In Li 3Cu 2O 4, the copper was oxidised to the III level when cycling. The replacement of the lithium by the sodium ions in the octahedral sites in Li 2NaCu 2O 4 might have an effect on the pathway of the lithium ions during the (de)intercalations.

Stability of Li- and Mn-Rich Layered-Oxide Cathodes within the First-Charge Voltage Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iddir, Hakim; Bareño, Javier; Benedek, Roy

Li and Mn rich layered oxides xLi 2MnO 3•(1-x)LiMO 2 enable high capacity and energy density Li-ion batteries, but undergo structural transformations during the first charge that degrade their performance, and result in Voltage Fade upon cycling. First-principles density-functional-theory simulations reveal atomic transformations that occur in the bulk during the first charge. The simulations and experiment (particularly XRD) show that the O and Mn sublattices remain intact during the early part of the voltage plateau, and significant transformations occur only well into the voltage plateau, with perhaps close to half of the Li in the Li 2MnO 3 domains removed.more » That Voltage Fade is actually observed experimentally for a first charge with only minimal activation (extending only slightly beyond the onset of the voltage plateau) may be a consequence of surface and interface instabilities. Implications for the achievement of high energy-density, low-fade battery operation are discussed.« less

Designing High Capacity, Stable Lithium-Manganese Oxide Insertion Electrodes with First Principles Computations

NASA Astrophysics Data System (ADS)

Reed, John; van der Ven, Anton; Ceder, Gerbrand

2001-03-01

The viability of rechargeable lithium batteries in many applications hinges on finding electrode materials with high capacity, excellent chemical and phase stability, and low cost. LiCoO_2, the intercalation oxide currently used is too expensive and unsafe for large-scale batteries. Manganese oxides are a possible low cost alternative, but spinel LiMn_2O _4, the common form of the material, has too low a capacity and some stability problems. Recently, layered LiMnO _2, isostructural to LiCoO _2, has been synthesized. After a few battery cycles this material irreversibly transforms to a spinel structure, with loss of battery capacity. In this work we use Density Functional Theory to investigate why LiMnO2 transforms so rapidly to spinel but LiCoO 2 does not, even though both are known to be thermodynamically unstable towards this transformation. We find that the difference between the two compound is due to remarkably rapid diffusion of Mn ^3+. Diffusion of Mn^3+ occurs by disproportionation into Mn ^2+ an Mn ^4+ which gives the system a remarkable flexibility in its hybridization with the oxygen ions, even at the saddle point for diffusion. This knowledge has now been used to suggest compositional modifications of LiMnO 2 which slow down or even prevent the transformation to a spinel.

Structure and electrochemical performance of Li[Ni(1 -x-y)Co(x)Mn(y)]O2 [0.025 < or = x < or = 0.4, 0.015 < or = y < or = 0.25] as cathodes compound for lithium ion batteries.

PubMed

Choi, Y G; Kim, D H; Im, J S; Kang, J W; Kim, E J; Kim, J

2008-10-01

Li[Ni(1-x-y)Co(x)Mn(y)]O2 (0.025 < or = x < or = 0.4, 0.015 < or = y < or = 0.25) electrode powders were prepared by a solid-state reaction. The phase purity and R-3m layered structure of the synthesized Li[Ni(1-x-y)Co(x)Mn(y)]O2 materials were confirmed by X-ray diffraction analysis. The particle size of the powder/compounds was decreased with increasing Co and Mn contents to a minimum average particle size of 0.2 approximately 0.3 microm for the LiNi0.35Co0.4Mn0.25O2 powder. A specific capacity of 187 mAh/g was obtained for the LiNi0.35Co0.4Mn0.25O2 electrode with good capacity retention when cycled in the potential region of 3.0-4.6 V with a current density of 20 mA/g at room temperature. Although the structural parameters of the LiNi0.35Co0.4Mn0.25O2 cathode material were similar to those of the LiNil/3CO1/3Mn1/3O2 powder, its specific capacity was higher due to the higher Co contents.

Sputtering graphite coating to improve the elevated-temperature cycling ability of the LiMn2O4 electrode.

PubMed

Wang, Jiexi; Zhang, Qiaobao; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Xu, Daguo; Zhang, Kaili

2014-08-14

To improve the cycle performance of LiMn2O4 at elevated temperature, a graphite layer is introduced to directly cover the surface of a commercial LiMn2O4-based electrode via room-temperature DC magnetron sputtering. The as-modified cathodes display improved capacity retention as compared to the bare LiMn2O4 cathode (BLMO) at 55 °C. When sputtering graphite for 30 min, the sample shows the best cycling performance at 55 °C, maintaining 96.2% capacity retention after 200 cycles. Reasons with respect to the graphite layer for improving the elevated-temperature performance of LiMn2O4 are systematically investigated via the methods of cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectrometry, scanning and transmission electron microscopy, X-ray diffraction and inductively coupled plasma-atomic emission spectrometry. The results demonstrate that the graphite coated LiMn2O4 cathode has much less increased electrode polarization and electrochemical impedance than BLMO during the elevated-temperature cycling process. Furthermore, the graphite layer is able to alleviate the severe dissolution of manganese ions into the electrolyte and mitigate the morphological and structural degradation of LiMn2O4 during cycling. A model for the electrochemical kinetics process is also suggested for explaining the roles of the graphite layer in suppressing the Mn dissolution.

Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li0.2Ni0.2Mn0.6]O2.

PubMed

Luo, Kun; Roberts, Matthew R; Guerrini, Niccoló; Tapia-Ruiz, Nuria; Hao, Rong; Massel, Felix; Pickup, David M; Ramos, Silvia; Liu, Yi-Sheng; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

2016-09-07

Conventional intercalation cathodes for lithium batteries store charge in redox reactions associated with the transition metal cations, e.g., Mn(3+/4+) in LiMn2O4, and this limits the energy storage of Li-ion batteries. Compounds such as Li[Li0.2Ni0.2Mn0.6]O2 exhibit a capacity to store charge in excess of the transition metal redox reactions. The additional capacity occurs at and above 4.5 V versus Li(+)/Li. The capacity at 4.5 V is dominated by oxidation of the O(2-) anions accounting for ∼0.43 e(-)/formula unit, with an additional 0.06 e(-)/formula unit being associated with O loss from the lattice. In contrast, the capacity above 4.5 V is mainly O loss, ∼0.08 e(-)/formula. The O redox reaction involves the formation of localized hole states on O during charge, which are located on O coordinated by (Mn(4+)/Li(+)). The results have been obtained by combining operando electrochemical mass spec on (18)O labeled Li[Li0.2Ni0.2Mn0.6]O2 with XANES, soft X-ray spectroscopy, resonant inelastic X-ray spectroscopy, and Raman spectroscopy. Finally the general features of O redox are described with discussion about the role of comparatively ionic (less covalent) 3d metal-oxygen interaction on anion redox in lithium rich cathode materials.

Enhancement in multiple lignolytic enzymes production for optimized lignin degradation and selectivity in fungal pretreatment of sweet sorghum bagasse.

PubMed

Mishra, Vartika; Jana, Asim K; Jana, Mithu Maiti; Gupta, Antriksh

2017-07-01

The objective of this work was to study the increase in multiple lignolytic enzyme productions through the use of supplements in combination in pretreatment of sweet sorghum bagasse (SSB) by Coriolus versicolor such that enzymes act synergistically to maximize the lignin degradation and selectivity. Enzyme activities were enhanced by metallic salts and phenolic compound supplements in SSF. Supplement of syringic acid increased the activities of LiP, AAO and laccase; gallic acid increased MnP; CuSO 4 increased laccase and PPO to improve the lignin degradations and selectivity individually, higher than control. Combination of supplements optimized by RSM increased the production of laccase, LiP, MnP, PPO and AAO by 17.2, 45.5, 3.5, 2.4 and 3.6 folds respectively for synergistic action leading to highest lignin degradation (2.3 folds) and selectivity (7.1 folds). Enzymatic hydrolysis of pretreated SSB yielded ∼2.43 times fermentable sugar. This technique could be widely applied for pretreatment and enzyme productions. Copyright © 2017 Elsevier Ltd. All rights reserved.

New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

PubMed Central

Chen, Liang; Gu, Qingwen; Zhou, Xufeng; Lee, Saixi; Xia, Yonggao; Liu, Zhaoping

2013-01-01

Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation. PMID:23736113

Charge and orbital orders and structural instability in high-pressure quadruple perovskite CeCuMn6O12

NASA Astrophysics Data System (ADS)

Zhang, Lei; Matsushita, Yoshitaka; Katsuya, Yoshio; Tanaka, Masahiko; Yamaura, Kazunari; Belik, Alexei A.

2018-02-01

We prepared a quadruple perovskite CeCuMn6O12 under high-pressure and high-temperature conditions at 6 GPa and about 1670 K and investigated its structural, magnetic and transport properties. CeCuMn6O12 crystallizes in space group Im-3 above T CO  =  297 K below this temperature, it adopts space group R-3 with the 1:3 (Mn4+:Mn3+) charge and orbital orders. Unusual compressed Mn3+O6 octahedra are realized in CeCuMn6O12 similar to CaMn7O12 with the  -Q 3 Jahn-Teller distortion mode. Below about 90 K, structural instability takes place with phase separation and the appearance of competing phases; and below 70 K, two R-3 phases coexist. CeCuMn6O12 exhibits a ferromagnetic-like transition below T C  =  140 K, and it is a semiconductor with the magnetoresistance reaching about  -40% at 140 K and 70 kOe. We argued that the valence of Ce is  +3 in CeCuMn6O12 with the Ce3+(C{{u}2+}Mn23+ )(Mn33+M{{n}4+} )O12 charge distribution in the charge-ordered R-3 phase and Ce3+(C{{u}2+}Mn23+ )(Mn43.25+ )O12 in the charge-disordered Im-3 phase.

Elastocaloric effect in CuAlZn and CuAlMn shape memory alloys under compression

PubMed Central

Qian, Suxin; Wang, Yi; Pillsbury, Thomas E.; Hada, Yoshiharu; Yamaguchi, Yuki; Fujimoto, Kenjiro; Hwang, Yunho; Radermacher, Reinhard; Cui, Jun; Yuki, Yoji; Toyotake, Koutaro; Takeuchi, Ichiro

2016-01-01

This paper reports the elastocaloric effect of two Cu-based shape memory alloys: Cu68Al16Zn16 (CuAlZn) and Cu73Al15Mn12 (CuAlMn), under compression at ambient temperature. The compression tests were conducted at two different rates to approach isothermal and adiabatic conditions. Upon unloading at a strain rate of 0.1 s−1 (adiabatic condition) from 4% strain, the highest adiabatic temperature changes (ΔTad) of 4.0 K for CuAlZn and 3.9 K for CuAlMn were obtained. The maximum stress and hysteresis at each strain were compared. The stress at the maximum recoverable strain of 4.0% for CuAlMn was 120 MPa, which is 70% smaller than that of CuAlZn. A smaller hysteresis for the CuAlMn alloy was also obtained, about 70% less compared with the CuAlZn alloy. The latent heat, determined by differential scanning calorimetry, was 4.3 J g−1 for the CuAlZn alloy and 5.0 J g−1 for the CuAlMn alloy. Potential coefficients of performance (COPmat) for these two alloys were calculated based on their physical properties of measured latent heat and hysteresis, and a COPmat of approximately 13.3 for CuAlMn was obtained. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402936

Outstanding laser damage threshold in Li2MnGeS4 and tunable optical nonlinearity in diamond-like semiconductors.

PubMed

Brant, Jacilynn A; Clark, Daniel J; Kim, Yong Soo; Jang, Joon I; Weiland, Ashley; Aitken, Jennifer A

2015-03-16

The new Li2MnGeS4 and Li2CoSnS4 compounds result from employing a rational and simple design strategy that guides the discovery of diamond-like semiconductors (DLSs) with wide regions of optical transparency, high laser damage threshold, and efficient second-order optical nonlinearity. Single-crystal X-ray diffraction was used to solve and refine the crystal structures of Li2MnGeS4 and Li2CoSnS4, which crystallize in the noncentrosymmetric space groups Pna21 and Pn, respectively. Synchrotron X-ray powder diffraction (SXRPD) was used to assess the phase purity, and diffuse reflectance UV-vis-NIR spectroscopy was used to estimate the bandgaps of Li2MnGeS4 (Eg = 3.069(3) eV) and Li2CoSnS4 (Eg = 2.421(3) eV). In comparison with Li2FeGeS4, Li2FeSnS4, and Li2CoSnS4 DLSs, Li2MnGeS4 exhibits the widest region of optical transparency (0.60-25 μm) and phase matchability (≥1.6 μm). All four of the DLSs exhibit second-harmonic generation and are compared with the benchmark NLO material, AgGaSe2. Most remarkably, Li2MnGeS4 does not undergo two- or three-photon absorption upon exposure to a fundamental Nd:YAG beam (λ = 1.064 μm) and exhibits a laser damage threshold > 16 GW/cm(2).

Andromeda polifolia and Oxycoccus microcarpus as pollution indicators for ombrotrophic bogs in the Western Sudety Mountains (SW Poland).

PubMed

Wojtuń, Bronisław; Samecka-Cymerman, Aleksandra; Kolon, Krzysztof; Klink, Agnieszka; Kempers, Alexander J

2013-01-01

Concentrations of the elements Cd, Cr, Cu, Fe, Li, Mn, N, Ni, Pb and Zn in Andromeda polifolia, Oxycoccus microcarpus and in the peat in which these plants grew were measured in the Western Sudety (Karkonosze and Izerskie Mts., SW Poland). Of both the investigated plant fruit, O. microcarpus harvested from wild populations are commonly used as medicines. Samples from ombrotrophic bogs were investigated within the area influenced by exhausts of the former Black Triangle, one of the most heavily industrialized and polluted areas in Europe. A. polifolia and O. microcarpus growing at the highest elevations contained the highest Cu, Li, Ni, Mn and Zn concentrations and in addition O. microcarpus also contained the highest Cr concentrations. Both the investigated species have wide circumpolar distribution in ombrotrophic mires of the Northern hemisphere. As this type of mires is nourished solely by atmospheric deposition, the increased metal concentrations in A. polifolia and O. microcarpus may be an indication that their habitats receive an atmospheric input of long-range transported pollution. Our investigation proves that both species are able to accumulate elevated metal levels and may be used in the bioindication of the metal status in ombrotrophic mires. Controlling the collection of O. microcarpus fruit for consumption and medicinal purposes is recommended as this species can accumulate increased metal levels. However, further more detailed studies are necessary to verify the inner translocation of metals into fruit.

Investigations on the direct introduction of cigarette smoke for trace elements analysis by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chang, Michael J.; Naworal, John D.; Walker, Kathleen; Connell, Chris T.

2003-11-01

Direct introduction of mainstream cigarette smoke into an inductively coupled plasma mass spectrometry (ICP-MS) has been investigated with respect to its feasibility for on-line analysis of trace elements. An automated apparatus was designed and built interfacing a smoking machine with an ICP-MS for smoke generation, collection, injection and analysis. Major and minor elements present in the particulate phase and the gas phase of mainstream cigarette smoke of 2R4F reference cigarettes have been qualitatively identified by examination of their full mass spectra. This method provides a rapid-screening analysis of the transfer of trace elements into mainstream smoke during cigarette combustion. A full suite of elements present in the whole cigarette smoke has been identified, including As, B, Ba, Br, Cd, Cl, Cs, Cu, Hg, I, K, Li, Mn, Na, Pb, Rb, Sb, Sn, Tl and Zn. Of these elements, the major portions of B, Ba, Cs, Cu, K, Li, Mn, Na, Pb, Rb, Sn, Tl and Zn are present in the particulate phase, whereas the major portion of Hg is present in the gas phase. As, Br, Cd, Cl, I and Sb exist in a distribution between the gas phase and the particulate phase. Depending on the element, the precision of measurement ranges from 5 to 25% in terms of relative standard deviation of peak height and peak area, based on the fourth puff of 2R4F mainstream cigarette smoke analyzed in five smoking replicates.

Characterisation of a natural quartz crystal as a reference material for microanalytical determination of Ti, Al, Li, Fe, Mn, Ga and Ge

USGS Publications Warehouse

Audetat, Andreas; Garbe-Schonberg, Dieter; Kronz, Andreas; Pettke, Thomas; Rusk, Brian G.; Donovan, John J.; Lowers, Heather

2015-01-01

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP-MS, electron probe microanalysis (EPMA) and solution ICP-MS to determine the concentration of twenty-four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium-in-quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA-ICP-MS laboratories, three EPMA laboratories and one solution-ICP-MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g-1), Al (154 ± 15 μg g-1), Li (30 ± 2 μg g-1), Fe (2.2 ± 0.3 μg g-1), Mn (0.34 ± 0.04 μg g-1), Ge (1.7 ± 0.2 μg g-1) and Ga (0.020 ± 0.002 μg g-1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.

Synthesis and characterization of integrated layered nanocomposites for lithium ion batteries

PubMed Central

2012-01-01

The series of Li[NixMxLi1/3-xMn2/3-x]O2 cathodes, where M is cobalt or chromium with a wide compositional range x from 0 to 0.33, were prepared by hydroxide coprecipitation method with subsequent quenching. The sample structures were investigated using X-ray diffraction results which were indexed completely on the basis of a trigonal structure of space group R3m¯ with monoclinic C2/m phase as expected. The morphologies and electrochemical properties of the samples obtained were compared as the value of x and substituted transition metal. The particle sizes of cobalt-substituted Li[NixCoxLi1/3-xMn2/3-x]O2 samples are much smaller than those of the Li[NixCrxLi1/3-xMn2/3-x]O2 system. The electrode containing Li[NixCoxLi1/3-xMn2/3-x]O2 with x = 0.10 delivered a discharge capacity of above 200 mAh/g after 10 cycles due to the activation of Li2MnO3. PACS: 82.47.Aa; 82.47.-a; 82.45.Fk. PMID:22221827

Al-Cu-Li and Al-Mg-Li alloys: Phase composition, texture, and anisotropy of mechanical properties (Review)

NASA Astrophysics Data System (ADS)

Betsofen, S. Ya.; Antipov, V. V.; Knyazev, M. I.

2016-04-01

The results of studying the phase transformations, the texture formation, and the anisotropy of the mechanical properties in Al-Cu-Li and Al-Mg-Li alloys are generalized. A technique and equations are developed to calculate the amounts of the S1 (Al2MgLi), T1 (Al2CuLi), and δ' (Al3Li) phases. The fraction of the δ' phase in Al-Cu-Li alloys is shown to be significantly higher than in Al-Mg-Li alloys. Therefore, the role of the T1 phase in the hardening of Al-Cu-Li alloys is thought to be overestimated, especially in alloys with more than 1.5% Li. A new model is proposed to describe the hardening of Al-Cu-Li alloys upon aging, and the results obtained with this model agree well with the experimental data. A texture, which is analogous to that in aluminum alloys, is shown to form in sheets semiproducts made of Al-Cu-Li and Al-Mg-Li alloys. The more pronounced anisotropy of the properties of lithium-containing aluminum alloys is caused by a significant fraction of the ordered coherent δ' phase, the deformation mechanism in which differs radically from that in the solid solution.

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes

PubMed Central

Devaraj, A.; Gu, M.; Colby, R.; Yan, P.; Wang, C. M.; Zheng, J. M.; Xiao, J.; Genc, A.; Zhang, J. G.; Belharouak, I.; Wang, D.; Amine, K.; Thevuthasan, S.

2015-01-01

The distribution of cations in Li-ion battery cathodes as a function of cycling is a pivotal characteristic of battery performance. The transition metal cation distribution has been shown to affect cathode performance; however, Li is notoriously challenging to characterize with typical imaging techniques. Here laser-assisted atom probe tomography (APT) is used to map the three-dimensional distribution of Li at a sub-nanometre spatial resolution and correlate it with the distribution of the transition metal cations (M) and the oxygen. As-fabricated layered Li1.2Ni0.2Mn0.6O2 is shown to have Li-rich Li2MO3 phase regions and Li-depleted Li(Ni0.5Mn0.5)O2 regions. Cycled material has an overall loss of Li in addition to Ni-, Mn- and Li-rich regions. Spinel LiNi0.5Mn1.5O4 is shown to have a uniform distribution of all cations. APT results were compared to energy dispersive spectroscopy mapping with a scanning transmission electron microscope to confirm the transition metal cation distribution. PMID:26272722

Design rules of heteroatom-doped graphene to achieve high performance lithium-sulfur batteries: Both strong anchoring and catalysing based on first principles calculation.

PubMed

Zhang, Lin; Liang, Pei; Shu, Hai B; Man, Xiao L; Du, Xiao Q; Chao, Dong L; Liu, Zu G; Sun, Yu P; Wan, Hou Z; Wang, Hao

2018-06-18

A number of observations have been reported on chemical capture and catalysis of anchoring materials for lithium-sulfur batteries. Here, we propose the design principles for the chemical functioned graphene as an anchor material to realize both strong chemical trapping and catalysis. Through the first principle, the periodic law is calculated from the theory. Seven different co-doping series were investigated, e.g. MN 4 @graphene (M = V, Cr, Mn, Fe, Co, Ni, and Cu). From binding energy, partial density of state, and charge density difference analysis, the FeN 4 and CrN 4 co-doped graphene show good performance for the lithium-sulfur battery from both strong anchoring and catalytic effects. For the most kinds of Li 2 S x (x = 1, 2, 4, 6, 8) absorption, two combinations can be achieved, including S-bonding and Li-bonding. The competition between the MS and the NLi shows the main difference of the co-doped configurations. Moreover, the S-bonding systems have better performance for both moderate chemical trapping and strong catalysis. The binding energies of Li 2 S x and Li decomposed properties considered as the key descriptors for the rational design of lithium-sulfur battery. Lastly, we offer design rules for high performance lithium-sulfur batteries based on the chemical functional graphene materials. Copyright © 2018 Elsevier Inc. All rights reserved.

(Cu,C)Ba2Ca3Cu4Ox (LiF)y: addition of LiF—an effective way to synthesize overdoped superconductor

NASA Astrophysics Data System (ADS)

Badica, P.; Iyo, A.; Aldica, G.; Kito, H.; Crisan, A.; Tanaka, Y.

2004-03-01

(Cu,C)Ba2Ca3Cu4Ox superconductor with addition of y mol LiF has been synthesized by a high-pressure method. For the same synthesis conditions it was found that (almost) single-phase Cu, C-1234 samples can be synthesized for yLiF = 0-0.1 if the amount of z mol AgO oxidizer is increased linearly from zAgO = 0.45 to 0.73 and for yLiF = 0.1-0.2 if zAgO = 0.73 = constant. Transport measurements (rgr(T) and room-temperature Seebeck coefficient) have shown that these samples are overdoped: LiF is an effective addition for synthesis of overdoped Cu, C-1234 with a controlled level of carriers. LiF addition continuously decreases Tc. The critical point at yLiF = 0.1 is discussed as the solubility limit of LiF and/or the point where the doping mechanism changes. It is proposed that the reason is the reaction of extra Li with C and O to form Li2CO3, inducing a lower concentration of C in Cu, C-1234/LiF crystals, and at the same time a possible substitution of Li not only for the Cu site but also for the Ca site, resulting in formation of a higher amount of residual Ca0.828CuO2 (for yLiF>0.1). LiF induces the formation of a liquid phase and acts as a flux promoting the formation of Cu,C-12 (n-1)n with n \\ge 4 . LiF modifies to some degree the grain growth from a 3D to a 2D type (thinner platelike grains have been observed in the LiF added samples).

Free standing CuO-MnO2 nanocomposite for room temperature ammonia sensing

NASA Astrophysics Data System (ADS)

Bhuvaneshwari, S.; Papachan, Seethal; Gopalakrishnan, N.

2017-05-01

CuO nanostructures and CuO-MnO2 nanocomposite were successfully synthesized using hydrothermal method without any aid of growth controlling agents. The synthesized CuO nanostructures have monoclinic structure. The XRD pattern of CuO-MnO2 observed with mixed phases of monoclinic CuO and birnessite-type MnO2 which confirms the formation of nanocomposite. SEM images revealed the turmeric-like morphology for CuO and intercalated sheets with flowers on the surface for CuO-MnO2. The length and breadth of turmeric-like structure is about 642.2 nm and 141.8 nm, respectively. The band gap of 1.72 eV for CuO nanostructure and 1.9 eV for CuO-MnO2 nanocomposite were observed from the absorption spectra. The free standing devices of CuO-MnO2 showed nearly a 3 fold increase sensing response to ammonia at room temperature when compared to the constituent CuO. The composite sensor showed response time of 120 s and recovered within 600 s. This enhanced response can be asserted to the peculiar morphology of the composite that provides more adsorption site for gas diffusion to take place.

Cation Ordering in Li[NixMnxCo(1-2x)]O2-Layered Cathode Materials: A Nuclear Magnetic Resonance (NMR), Pair Distribution Function, X-ray Absorption Spectroscopy, and Electrochemical Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng,D.; Cabana, J.; Breger, J.

2007-01-01

Several members of the compositional series Li[NixMnxCo(1-2x)]O2 (0.01 = x = 1/3) were synthesized and characterized. X-ray diffraction results confirm the presence of the layered a-NaFeO2-type structure, while X-ray absorption near-edge spectroscopy experiments verify the presence of Ni2+, Mn4+, and Co3+. Their local environment and short-range ordering were investigated by using a combination of 6Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and neutron pair distribution function (PDF) analysis, associated with reverse Monte Carlo (RMC) calculations. The 6Li MAS NMR spectra of compounds with low Ni/Mn contents (x = 0.10) show several well-resolved resonances, which start to mergemore » when the amount of Ni and Mn increases, finally forming a broad resonance at high Ni/Mn contents. Analysis of the 6Li MAS NMR 6Li[Ni0.02Mn0.02Co0.96]O2 spectrum, is consistent with the formation of Ni2+ and Mn4+ clusters within the transition-metal layers, even at these low-doping levels. The oxidation state of Ni in this high Co content sample strongly depends upon the Li/transition metal ratio of the starting materials. Neutron PDF analysis of the highest Ni/Mn content sample Li[Ni1/3Mn1/3Co1/3]O2 shows a tendency for Ni cations to be close to Mn cations in the first coordination shell; however, the Co3+ ions are randomly distributed. Analysis of the intensity of the 'LiCoO2' resonance, arising from Li surrounded by Co3+ in its first two cation coordination shells, for the whole series provides further evidence for a nonrandom distribution of the transition-metal cations. The presence of the insulator-to-metal transition seen in the electrochemical profiles of these materials upon charging correlates strongly with the concentration of the 'LiCoO2' resonance.« less

Morphological modification of alpha-MnO2 catalyst for use in Li/air batteries.

PubMed

Park, Min-Sik; Kim, Jae-Hun; Kim, Ki Jae; Jeong, Goojin; Kim, Young-Jun

2013-05-01

Single crystal alpha-MnO2 nanowires and nanopowders have been successfully synthesized in order to facilitate a comparison of their catalytic activity for use in Li-air batteries. The importance of the morphological modification of the alpha-MnO2 catalyst for facilitating electrochemical reactions between Li and O2 is addressed. Distinctive catalytic activity of alpha-MnO2 is observed, which is in line with its different morphologies. The catalytic activity significantly affects the reversible capacity of Li-air batteries. A high aspect ratio, large surface area and good dispersibility of alpha-MnO2 in the nanowire form are advantageous providing larger active surfaces for promoting the fundamental reactions in Li-air batteries. We also introduce a robustly designed air-electrode composed of highly porous carbon and nanostructured alpha-MnO2 catalysts, with employs a metal foam current collector to ensure sufficient air-permeability and to maximize electronic conduction during cycles. Our suggestions should prove helpful in forming a basis for further investigations in developing advanced Li-air batteries.

Capacity improvement by deficit of transition metals in inverse spinel LiNi1/3Co1/3Mn1/3VO4 cathodes

NASA Astrophysics Data System (ADS)

Kitajou, Ayuko; Yoshida, Jun; Nakanishi, Shinji; Matsuda, Yasuaki; Kanno, Ryoji; Okajima, Toshihiro; Okada, Shigeto

2016-01-01

Although inverse spinel materials have attracted attention because of their unusually high voltage characteristics, their rechargeable capacities are generally less than 50 mAh g-1, as a result of the coexistence of Li and transition metal ions at 16d octahedral sites. This work attempted to improve cathode functioning by optimizing the quantities of Li and transition metal ions residing at the 16d sites of LiNi1/3Co1/3Mn1/3VO4. The rechargeable capacity of the LiNi0.28Co0.28Mn0.26V0.80O4 synthesized in the present study was found to be above 120 mAh g-1, representing the largest capacity reported to date for an inverse spinel material. The results of in-situ XANES analysis demonstrated that the charge-discharge reactions of LiNi1/3Co1/3Mn1/3VO4 corresponds to the Mn2+/Mn4+ and Co2+/Co3+ redox couples, mainly.

Quantification of chemical elements in blood of patients affected by multiple sclerosis.

PubMed

Forte, Giovanni; Visconti, Andrea; Santucci, Simone; Ghazaryan, Anna; Figà-Talamanca, Lorenzo; Cannoni, Stefania; Bocca, Beatrice; Pino, Anna; Violante, Nicola; Alimonti, Alessandro; Salvetti, Marco; Ristori, Giovanni

2005-01-01

Although some studies suggested a link between exposure to trace elements and development of multiple sclerosis (MS), clear information on their role in the aetiology of MS is still lacking. In this study the concentrations of Al, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, Ni, Pb, Sb, Si, Sn, Sr, Tl, V, W, Zn and Zr were determined in the blood of 60 patients with MS and 60 controls. Quantifications were performed by inductively coupled plasma (ICP) atomic emission spectrometry and sector field ICP mass spectrometry. When the two groups were compared, an increased level of Co, Cu and Ni and a decrement of Be, Fe, Hg, Mg, Mo, Pb and Zn in blood of patients were observed. In addition, the discriminant analysis pointed out that Cu, Be, Hg, Co and Mo were able to discriminate between MS patients and controls (92.5% of cases correctly classified).

Effect of Nb and F co-doping on Li1.2Mn0.54Ni0.13Co0.13O2 cathode material for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ming, Lei; Zhang, Bao; Cao, Yang; Zhang, Jia-Feng; Wang, Chun-Hui; Wang, Xiao-Wei; Li, Hui

2018-04-01

The Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x (x=0, 0.01, 0.03, 0.05) is prepared by traditional solid-phase method, and the Nb and F ions have been successfully doped into Mn and O sites of layered materials Li1.2Mn0.54Co0.13Ni0.13O2, respectively. The incorporating Nb ion in Mn site could effectively restrain the migration of transtion metal ions during long-term cycling, and keep the stability of the crystal structure. The Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x shows suppressed voltage fade and higher capacity retention of 98.1 after 200 cycles at rate of 1 C. The replacement of O2- by the strongly electronegative F- was beneficial for suppressed the structure change of Li2MnO3 from the eliminating of oxygen in initial charge process. Therefore, the initial coulomb efficiency of doped Li1.2Mn0.54-xNbxCo0.13Ni0.13O2-6xF6x gets improved, which is higher than that of pure Li1.2Mn0.54Co0.13Ni0.13O2. In addition, the Nb and F co-doping could effectively enhance the transfer of lithium-ion and electrons, and thus improving rate performance.

Synthesis and electrochemical properties of 4LiF-NiMn2O4 composite as a cathode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Tomita, Yasumasa; Kimura, Noritaka; Izumi, Yusuke; Arai, Juichi; Kohno, Yoshiumi; Kobayashi, Kenkichiro

2017-06-01

4LiF-NiMn2O4 composites are synthesized by the mechanical milling of LiF and NiMn2O4 in a molar ratio of 4: 1 for 36-192 h. The synthesized composites are investigated by XRD, charge-discharge measurements, and XPS. A broad XRD peak of 4LiF-NiMn2O4 was observed and those of LiF and NiMn2O4 disappear after the milling of 144 h and more. The discharge capacity of the 4LiF-NiMn2O4 composites changes with the milling time, with the composite prepared by milling for 144 h exhibiting a discharge capacity of 256 mA h g-1 at 0.1 C for voltages of 2.0-4.8 V. With a cut-off voltage of 4.8 V or more, decomposition of the electrolyte proceeds along with the charge process, so the charge-discharge current efficiency deteriorates and the discharge voltage decreases. In the charge-discharge measurement without the capacity limit, although the charge-discharge efficiency was low due to the decomposition of the electrolyte, the high discharge capacity of 310 mA h g-1 was obtained. The XPS data suggests that the Ni2+ ion and Mn3+ ion are oxidized to Ni3+ and Mn4+ ion in charge process up to 4.8 V and are reduced to Ni2+ ion and Mn3+ ion during the discharge process.

Synthesis and electrochemical characterizations of spinel LiMn1.94MO4 (M = Mn0.06, Mg0.06, Si0.06, (Mg0.03Si0.03)) compounds as cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhao, Hongyuan; Liu, Xingquan; Cheng, Cai; Li, Qiang; Zhang, Zheng; Wu, Yue; Chen, Bing; Xiong, Weiqiang

2015-05-01

The spinel LiMn1.94MO4 (M = Mn0.06, Mg0.06, Si0.06, (Mg0.03Si0.03)) compounds are successfully synthesized by citric acid-assisted sol-gel method. The crystal structures and morphologies of synthesized compounds are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. All the compounds possess the cubic spinel structure of LiMn2O4 with space group of Fd-3m. The electrochemical properties of synthesized compounds are investigated by galvanostatic charge-discharge test, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that the Si-doping can increase the discharge capacity of LiMn2O4 due to the more expanded and regular MnO6 octahedra. In particular, for the LiMn1.94Mg0.03Si0.03O4 compound, the addition of Si4+ ions can make up for the shortage of Mg-doping in term of the discharge capacity. As a result, the Mg2+ and Si4+ co-doping has the effect of synergistic enhancement, which can make full use of the respective advantages of Mg-doping and Si-doping. The optimal LiMn1.94Mg0.03Si0.03O4 can deliver the initial discharge capacity of 128.3 mAh g-1 with good capacity retention of 92.8% after 100 cycles at 0.5 C in the voltage range of 3.20-4.35 V. Compared with the undoped LiMn2O4, the co-doped compound also presents superior rate performance, especially the capacity recovery performance.

Electronic Topological Transitions in CuNiMnAl and CuNiMnSn under pressure from first principles study

NASA Astrophysics Data System (ADS)

Rambabu, P.; Kanchana, V.

2018-06-01

A detailed study on quaternary ordered full Heusler alloys CuNiMnAl and CuNiMnSn at ambient and under different compressions is presented using first principles electronic structure calculations. Both the compounds are found to possess ferromagnetic nature at ambient with magnetic moment of Mn being 3.14 μB and 3.35 μB respectively in CuNiMnAl and CuNiMnSn. The total magnetic moment for both the compounds is found to decrease under compression. Fermi surface (FS) topology change is observed in both compounds under pressure at V/V0 = 0.90, further leading to Electronic Topological Transitions (ETTs) and is evidenced by the anomalies visualized in density of states and elastic constants under compression.

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

DOE PAGES

Li, Boyan; Zhang, Lei; Li, Chengliang; ...

2018-04-18

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

The effect of Mn/Ni on thermodynamic properties of critical nucleus in Fe-Cu-Mn (Ni) ternary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Boyan; Zhang, Lei; Li, Chengliang

The aging- or radiation-induced hardening of Cu/Mn/Ni precipitates in Fe alloys is one of property degradation mechanisms in structural materials in nuclear reactors. Experiments show that aging or radiation leads the formation of Cu-rich precipitates, and the addition of Mn or Ni elements enhances the precipitation kinetics. In this study, the phase-field model coupled with the constrained string method have been applied to investigate the thermodynamic properties of critical nuclei such as the minimum energy path of Cu/Mn/Ni precipitation in Fe-Cu-Mn and Fe-Cu-Ni ternary alloys. The chemical free energies used in the model are taken from CALPHAD. The simulation resultsmore » show that the formation of Cu/Mn/Ni clusters needs to overcome an energy barrier, and the precipitate has a Core-Shell structure. The thermodynamic properties of the critical nucleus are influenced by temperature and Cu/Mn/Ni overall concentrations, which are in accordance with the simulation results as well as the experimental observations.« less

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li xMn 2O 4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from Li xMn 2O 4 (100) surfaces

DOE PAGES

Leung, Kevin

2012-04-13

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; andmore » chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

PubMed

Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek; Nakai, Izumi; Komaba, Shinichi

2011-03-30

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

NASA Technical Reports Server (NTRS)

Sutter, B.; Wasowicz, T.; Howard, T.; Hossner, L. R.; Ming, D. W.

2002-01-01

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

Trace elements and radon in groundwater across the United States, 1992-2003

USGS Publications Warehouse

Ayotte, Joseph D.; Gronberg, Jo Ann M.; Apodaca, Lori E.

2011-01-01

Trace-element concentrations in groundwater were evaluated for samples collected between 1992 and 2003 from aquifers across the United States as part of the U.S. Geological Survey National Water-Quality Assessment Program. This study describes the first comprehensive analysis of those data by assessing occurrence (concentrations above analytical reporting levels) and by comparing concentrations to human-health benchmarks (HHBs). Data from 5,183 monitoring and drinking-water wells representing more than 40 principal and other aquifers in humid and dry regions and in various land-use settings were used in the analysis. Trace elements measured include aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), uranium (U), vanadium (V), and zinc (Zn). Radon (Rn) gas also was measured and is included in the data analysis. Climate influenced the occurrence and distribution of trace elements in groundwater whereby more trace elements occurred and were found at greater concentrations in wells in drier regions of the United States than in humid regions. In particular, the concentrations of As, Ba, B, Cr, Cu, Mo, Ni, Se, Sr, U, V, and Zn were greater in the drier regions, where processes such as chemical evolution, ion complexation, evaporative concentration, and redox (oxidation-reduction) controls act to varying degrees to mobilize these elements. Al, Co, Fe, Pb, and Mn concentrations in groundwater were greater in humid regions of the United States than in dry regions, partly in response to lower groundwater pH and (or) more frequent anoxic conditions. In groundwater from humid regions, concentrations of Cu, Pb, Rn, and Zn were significantly greater in drinking-water wells than in monitoring wells. Samples from drinking-water wells in dry regions had greater concentrations of As, Ba, Pb, Li, Sr, V, and Zn, than samples from monitoring wells. In humid regions, however, concentrations of most trace elements were greater in monitoring wells than in drinking-water wells; the exceptions were Cu, Pb, Zn, and Rn. Cu, Pb, and Zn are common trace elements in pumps and pipes used in the construction of drinking-water wells, and contamination from these sources may have contributed to their concentrations. Al, Sb, Ba, B, Cr, Co, Fe, Mn, Mo, Ni, Se, Sr, and U concentrations were all greater in monitoring wells than in drinking-water wells in humid regions. Groundwater from wells in agricultural settings had greater concentrations of As, Mo, and U than groundwater from wells in urban settings, possibly owing to greater pH in the agricultural wells. Significantly greater concentrations of B, Cr, Se, Ag, Sr, and V also were found in agricultural wells in dry regions. Groundwater from dry-region urban wells had greater concentrations of Co, Fe, Pb, Li, Mn, and specific conductance than groundwater from agricultural wells. The geologic composition of aquifers and aquifer geochemistry are among the major factors affecting trace-element occurrence. Trace-element concentrations in groundwater were characterized in aquifers from eight major groups based on geologic material, including (1) unconsolidated sand and gravel; (2) glacial unconsolidated sand and gravel; (3) semiconsolidated sand; (4) sandstone; (5) sandstone and carbonate rock; (6) carbonate rock; (7) basaltic and other volcanic rock; and (8) crystalline rock. The majority of groundwater samples and the largest percentages of exceedences of HHBs were in the glacial and nonglacial unconsolidated sand and gravel aquifers; in these aquifers, As, Mn, and U are the most common trace elements exceeding HHBs. Overall, 19 percent of wells (962 of 5,097) exceeded an HHB for at least one trace element. The trace elements with HHBs included in this summary were Sb, As, Ba, Be, B, Cd, Cr,

Ce3+ doping into 0.6Li2MnO3·0.4LiNi0.5Co0.2Mn0.3O2 as cathode material for Li-ion batteries applied in new energy vehicle

NASA Astrophysics Data System (ADS)

Peng, Han; Yao, Linxiao; Zhang, Ming

2018-06-01

The pristine Li1.20[Mn0.52Ni0.20Co0.08]O2 and Ce3+-doped Li1.20[Mn0.50Ni0.20Co0.08Ce0.02]O2 cathode materials have been synthesized by using the typical sol-gel method. The XRD, SEM, ICP-OES and galvanostatic charge-discharge tests were carried out to study the influence of Ce3+ doping on the crystal structural, morphology and electrochemical properties of Li1.20Mn0.54Ni0.13Co0.13O2. The XRD result revealed the Ce3+ doping modification could decrease the cation mixing degree. The galvanostatic charge-discharge tests results showed that the sample after Ce3+ doping demonstrated the smaller irreversible capacity loss, more stable cyclic performance and better rate capacity than those of the pristine one.

Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Armstrong, A. Robert; Bruce, Peter G.

1996-06-01

RECHARGEABLE lithium batteries can store more than twice as much energy per unit weight and volume as other rechargeable batteries1,2. They contain lithium ions in an electrolyte, which shuttle back and forth between, and are intercalated by, the electrode materials. The first commercially successful rechargeable lithium battery3, introduced by the Sony Corporation in 1990, consists of a carbon-based negative electrode, layered LiCoO2 as the positive electrode, and a non-aqueous liquid electrolyte. The high cost and toxicity of cobalt compounds, however, has prompted a search for alternative materials that intercalate lithium ions. One such is LiMn2O4, which has been much studied as a positive electrode material4-7 the cost of manganese is less than 1% of that of cobalt, and it is less toxic. Here we report the synthesis and electrochemical performance of a new material, layered LiMnO2, which is structurally analogous to LiCoO2. The charge capacity of LiMnO2 (~270mAhg-1) compares well with that of both LiCoO2 and LiMn2O4, and preliminary results indicate good stability over repeated charge-discharge cycles.

Doping effects on the relaxation of frustration and magnetic properties of YMn0.9Cu0.1O3

NASA Astrophysics Data System (ADS)

Xiao, L. X.; Xia, Z. C.; Wang, X.; Ni, Y.; Yu, W.; Shi, L. R.; Jin, Z.; Xiao, G. L.

2017-12-01

The crystal structure and magnetic properties of hexagonal YMn0.9Cu0.1O3 single crystal are systematically investigated. The refinement results of XRD show the lattice constant decreases, which is unusually due to the doped Cu2+ ion has a larger ionic radius than the Mn3+ ions. The XPS results show that the coexistence of Mn2+, Mn3+ and Mn4+ ions in YMn0.9Cu0.1O3 single crystal. Magnetization measurements show that Cu doped YMn0.9Cu0.1O3 and parent YMnO3 have almost the same antiferromagnetic transition temperature TN, which indicates the AFM interaction is robust in the geometry frustrated system. Because doping directly destroy some of the Mn3+ ions nets, the relaxation of frustration of Mn in-plane 2D triangular geometry network leads to the significantly decrease of Mn3+ ions AFM interaction. In addition, the coexistence and competition between the ferromagnetic and antiferromagnetic interactions among the Mn2+, Mn3+ and Mn4+ ions lead to a complicated and irreversible magnetization behavior in YMn0.9Cu0.1O3 single crystal.

Structural and electrochemical characterization and surface modification of layered solid solution oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Wu, Yan

Lithium ion batteries are widely used to power portable electronic devices such as cell phones and laptop computers due to their high energy density. However, the currently used layered LiCoO2 cathode could deliver only 50 % of its theoretical capacity in practical lithium ion cells (140 mAh/g) due to the chemical and structural instabilities at deep charge with (1-x) < 0.5 in Li1-xCoO2. Also, cobalt is relatively expensive and toxic. These difficulties have generated enormous interest in alternative cathode hosts. In this regard, solid solutions between layered Li[Li1/3Mn2/3]O2 (commonly designated as Li2MnO3) and LiMO2 (M = Mn, Ni, Co)) have become appealing as some of them exhibit much higher capacity (˜ 250 mAh/g on charging to 4.8 V) with lower cost and better safety compared to LiCoO 2. This dissertation investigates the (1-z) Li[Li1/3Mn 2/3]O2 - (z) Li[Mn0.5-yNi0.5-yCo 2y]O2 (y = 1/12, 1/6 and 1/3 and 0.25 = z = 0.75) layered oxide cathodes, which belong to a solid solution series between layered Li[Li 1/3Mn2/3]O2 and Li[Mn0.5-yNi0.5-y Co2y]O2, with an aim to develop a better understanding of the charge-discharge mechanisms and optimize the electrochemical performance of these materials. To accomplish this, the structural and electrochemical characterization of the (1- z) Li[Li1/3Mn2/3]O2 - (z) Li[Mn 0.5-yNi0.5-yCo2y]O2 cathodes is carried out. It is found that the amount of oxygen loss is related to the lithium content in the transition metal layer, and the Co and Mn4+ contents play a role in influencing the electrochemical behavior. In addition, the chemically delithiated samples are found to transform to O1 or P3 structure with a vanishing of the superlattice reflections arising from cationic ordering in the transition metal layer due to the incorporation of protons from the chemical delithiation medium, while the electrochemically charged samples retain the initial O3 structure. These layered solid solution oxides exhibit high irreversible capacity (IRC) loss (difference between first charge and discharge capacity) values (up to 100 mAh/g), which have been reduced significantly by modifying the cathode surface with other materials like Al2O3, AlPO 4, and F-. For example, compared to an IRC of 75 mAh/g and a first discharge capacity of 253 mAh/g for the pristine Li[Li0.2 Mn0.54Ni0.13Co0.13]O2 (y = 1/6 and z = 0.4), the 3 wt. % Al2O3 modified sample exhibits a lower IRC of 41 mAh/g and a higher first discharge capacity of 285 mAh/g, which is two times higher than that achieved with the LiCoO 2 cathode. A careful and systematic analysis of the experimentally observed capacity and IRC values suggest that part of the oxide ion vacancies created during first charge is retained in the layered lattice in contrast to the idealized model (elimination of all oxide ion vacancies) proposed in the literature. The surface modification helps to retain even more number of oxide ion vacancies in the lattice, which leads to a lower IRC and higher discharge capacity values. Additionally, bulk cationic and anionic substitutions of Al3+ and F- in Li[Li0.17Mn0.58Ni0.25 ]O2 (y = 0 and z = 0.5) are found to sensitively decrease the amount of oxygen loss from the lattice.

Growth behavior of LiMn{sub 2}O{sub 4} particles formed by solid-state reactions in air and water vapor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozawa, Takahiro, E-mail: t-kozawa@jwri.osaka-u.ac.jp; Yanagisawa, Kazumichi; Murakami, Takeshi

Morphology control of particles formed during conventional solid-state reactions without any additives is a challenging task. Here, we propose a new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles based on water vapor-induced growth of particles during solid-state reactions. We have investigated the synthesis and microstructural evolution of LiMn{sub 2}O{sub 4} particles in air and water vapor atmospheres as model reactions; LiMn{sub 2}O{sub 4} is used as a low-cost cathode material for lithium-ion batteries. By using spherical MnCO{sub 3} precursor impregnated with LiOH, LiMn{sub 2}O{sub 4} spheres with a hollow structure were obtained in air, while angulated particlesmore » with micrometer sizes were formed in water vapor. The pore structure of the particles synthesized in water vapor was found to be affected at temperatures below 700 °C. We also show that the solid-state reaction in water vapor is a simple and valuable method for the large-scale production of particles, where the shape, size, and microstructure can be controlled. - Graphical abstract: This study has demonstrated a new strategy towards achieving morphology control without the use of additives during conventional solid-state reactions by exploiting water vapor-induced particle growth. - Highlights: • A new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles is proposed. • Water vapor-induced particle growth is exploited in solid-state reactions. • The microstructural evolution of LiMn{sub 2}O{sub 4} particles is investigated. • The shape, size and microstructure can be controlled by solid-state reactions.« less

Composition and structure of acid leached LiMn 2-yTi yO 4 (0.2≤ y≤1.5) spinels

NASA Astrophysics Data System (ADS)

Avdeev, Georgi; Amarilla, José Manuel; Rojo, José María; Petrov, Kostadin; Rojas, Rosa María

2009-12-01

Lithium manganese titanium spinels, LiMn 2-yTi yO 4, (0.2≤ y≤1.5) have been synthesized by solid-state reaction between TiO 2 (anatase), Li 2CO 3 and MnCO 3. Li + was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li + leached from LiMn 2-yTi yO 4 decreases monotonically with increasing y in the interval 0.2≤ y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li + removal has been proposed.

General Approach to Prepare 0.33Li₂MnO₃ · 0.67LiNi1/3Co1/3Mn1/3O₂ Hollow Microspheres for High Performance Lithium Ion Batteries.

PubMed

Li, Jingfa; Xu, Wenjin; Zhang, Lei; Li, Min

2018-06-01

Li-excess manganese-based oxide layered structures, have drawn increasing interests as the promising cathodes to succeed the conventional LiCoO2 in lithium ion batteries (LIBs). It could deliver a higher energy density and output potential, as well as the nature of environment benign and low cost. Pristine Li-excess manganese-based oxides however suffer from poor rate capacity and voltage fading after cycling, and their inherent capacity limits of bulk size in performance. Micro-/Nanostructured electrode materials are considered to hold the key to overcome these thresholds. This paper reports a general approach to prepare 0.33Li2MnO3 · 0.67LiNi1/3Co1/3Mn1/3O2 microspheres with pores and void space, which benefits improving both the capacity and cyclability. The electrode made of hollow 0.33Li2MnO3 · 0.67LiNi1/3Co1/3Mn1/3O2 microspheres exhibits a 224 mAh g-1 discharge capacity over 200 cycles at 0.25 C rate, and 195 mAh g-1 at 5.0 C rate. These results indicated good perspective of hollow microspheres for practical battery applications.

Leaching process for recovering valuable metals from the LiNi1/3Co1/3Mn1/3O2 cathode of lithium-ion batteries.

PubMed

He, Li-Po; Sun, Shu-Ying; Song, Xing-Fu; Yu, Jian-Guo

2017-06-01

In view of the importance of environmental protection and resource recovery, recycling of spent lithium-ion batteries (LIBs) and electrode scraps generated during manufacturing processes is quite necessary. An environmentally sound leaching process for the recovery of Li, Ni, Co, and Mn from spent LiNi 1/3 Co 1/3 Mn 1/3 O 2 -based LIBs and cathode scraps was investigated in this study. Eh-pH diagrams were used to determine suitable leaching conditions. Operating variables affecting the leaching efficiencies for Li, Ni, Co, and Mn from LiNi 1/3 Co 1/3 Mn 1/3 O 2 , such as the H 2 SO 4 concentration, temperature, H 2 O 2 concentration, stirring speed, and pulp density, were investigated to determine the most efficient conditions for leaching. The leaching efficiencies for Li, Ni, Co, and Mn reached 99.7% under the optimized conditions of 1M H 2 SO 4 , 1vol% H 2 O 2 , 400rpm stirring speed, 40g/L pulp density, and 60min leaching time at 40°C. The leaching kinetics of LiNi 1/3 Co 1/3 Mn 1/3 O 2 were found to be significantly faster than those of LiCoO 2 . Based on the variation in the weight fraction of the metal in the residue, the "cubic rate law" was revised as follows: θ(1-f) 1/3 =(1-kt/r 0 ρ), which could characterize the leaching kinetics optimally. The activation energies were determined to be 64.98, 65.16, 66.12, and 66.04kJ/mol for Li, Ni, Co, and Mn, respectively, indicating that the leaching process was controlled by the rate of surface chemical reactions. Finally, a simple process was proposed for the recovery of valuable metals from spent LiNi 1/3 Co 1/3 Mn 1/3 O 2 -based LIBs and cathode scraps. Copyright © 2017 Elsevier Ltd. All rights reserved.

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

USGS Publications Warehouse

Symonds, R.B.; Rose, William I.; Reed, M.H.; Lichte, F.E.; Finnegan, David L.

1987-01-01

Condensates, silica tube sublimates and incrustations were sampled from 500-800??C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.-Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 105 in Se, Re, Bi and Cd; 104-105 in Au, Br, In, Pb and W; 103-104 in Mo, Cl, Cs, S, Sn and Ag; 102-103 in As, Zn, F and Rb; and 1-102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d) of S, Cl and F; 104-106 g/d of Al, Br, Zn, Fe, K and Mg; 103-104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500??C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915??C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit. ?? 1987.

Structural characterization of LiCrxMn2-xO4 via a simple reflux technique

NASA Astrophysics Data System (ADS)

Purwaningsih, Dyah; Roto, Roto; Sutrisno, Hari; Purwanto, Agus

2017-03-01

LiCrxMn2-xO4 (x=0; 0.02; 0.04; 0.06; 0.08, 0.10) have been successfully synthesized via a facile and simple reflux technique. The SEM-EDS data confirm the presence of Cr, Mn and O elements in the products, while the XRD pattern suggests that the materials have well-developed cubic crystals. Direct method was applied to extract structural parameters of LiCrxMn2-xO4 using the Fullprof and Oscail software in WinPlotr package program. Materials were refined in the crystal system, and space group of structures Fd3m phase were then identified. The lattice parameters decrease with the decrease in Cr content. The highest Li-O bond length was found for LiCr0.10Mn1.90O4. It was observed that there is no significant change in particle size as Cr content increased.

Solar photospheric and coronal abundances from solar energetic particle measurements. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Breneman, H.

1985-01-01

Observations of solar energetic particles (SEP) from 22 solar flares in the 1977 to 1982 time period are reported. SEP abundances were obtained for all elements with 3 approximately less than Z approximately less than 30 except Li, Be, B, F, Sc, v, Co and Cu for which upper limits were obtained. Statistically meaningful abundances of several rare elements (P, Cl, K, Ti, and Mn) were determined for the first time, and the average abundance of the more abundant elements were determined with improved precision.

Electrochemical performance of Li-rich oxide composite material coated with Li0.75La0.42TiO3 ionic conductor

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen; Liao, Pin-Ci; Wu, Yi-Shiuan; Lue, Shingjiang Jessie

2017-03-01

Li-rich (spray-dried (SP)-Li1.2Ni0.2Mn0.60O2) composite materials were prepared via two-step ball-mill and spray dry methods by using LiOH, α-MnO2, β-Ni(OH)2 raw materials. Two raw materials of α-MnO2 nanowires and microsphere β-Ni(OH)2 were synthesized by a hydrothermal process. In addition, Li0.75La0.42TiO3 (LLTO) fast ionic conductor was coated on SP-Li1.2Ni0.2Mn0.60O2 composite via a sol-gel method. The properties of the LLTO-coated SP-Li1.2Ni0.2Mn0.60O2 composites were determined by X-ray diffraction, scanning electron microscopy, micro-Raman, XPS, and the AC impedance method. The discharge capacities of 1 wt.%-LLTO-coated SP-Li1.2Ni0.2Mn0.60O2 composites were 256, 250, 231, 200, 158, and 114 mAh g-1 at rates of 0.1, 0.2, 0.5, 1, 3, and 5C, respectively, in the voltage range 2.0-4.8 V. The 1 wt.%-LLTO-coated Li-rich oxide composite showed the discharge capacities of up to 256 mAh g-1 in the first cycle at 0.1C. After 30 cycles, the discharge capacity of 244 mAh g-1 was obtained, which showed the capacity retention of 95.4%.

Electrochemical properties of copper-based compounds with polyanion frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota

The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed basedmore » on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.« less

Li-atoms-induced structure changes of Guinier–Preston–Bagaryatsky zones in AlCuLiMg alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, S.Y.; Le, Z.; Chen, Z.K.

2016-11-15

Guinier–Preston–Bagaryatsky (GPB) zones are the well-known strengthening precipitates of AlCuMg alloys formed upon thermal ageing. Here we report that when formed in AlCuLiMg alloys the GPB zones can change significantly in morphology and structure. It is shown that though they do still consist of Al, Cu and Mg elements fundamentally, the GPB zones in AlCuLiMg alloys have a rather different structure due to a featured Li-segregation at their interfaces with the matrix and possible Li-replacement of partial Mg atoms in the structure. As such the Li-containing GPB zones often develop from one-dimensional to quasi-two-dimensional precipitates. - Highlights: • We observemore » Guinier–Preston–Bagaryatsky zone variants in AlCuLiMg alloys. • We obtain atomic-resolution images of the precipitates and model their structures. • Li-atoms play a key role in modifying the structure of these precipitate variants.« less

Effect of Nb and F Co-doping on Li1.2Mn0.54Ni0.13Co0.13O2 Cathode Material for High-Performance Lithium-Ion Batteries

PubMed Central

Ming, Lei; Zhang, Bao; Cao, Yang; Zhang, Jia-Feng; Wang, Chun-Hui; Wang, Xiao-Wei; Li, Hui

2018-01-01

The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x (x = 0, 0.01, 0.03, 0.05) is prepared by traditional solid-phase method, and the Nb and F ions are successfully doped into Mn and O sites of layered materials Li1.2Mn0.54Co0.13Ni0.13O2, respectively. The incorporating Nb ion in Mn site can effectively restrain the migration of transition metal ions during long-term cycling, and keep the stability of the crystal structure. The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x shows suppressed voltage fade and higher capacity retention of 98.1% after 200 cycles at rate of 1 C. The replacement of O2− by the strongly electronegative F− is beneficial for suppressed the structure change of Li2MnO3 from the eliminating of oxygen in initial charge process. Therefore, the initial coulombic efficiency of doped Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x gets improved, which is higher than that of pure Li1.2Mn0.54Co0.13Ni0.13O2. In addition, the Nb and F co-doping can effectively enhance the transfer of lithium-ion and electrons, and thus improving rate performance. PMID:29675405

High voltage stable liquid electrolytes for Li 1+ xMn 2O 4/carbon rocking-chair lithium batteries

NASA Astrophysics Data System (ADS)

Guyomard, D.; Tarascon, J. M.

A high voltage oxidation-resistant electrolyte is required for Li 1+ xMn 2O 4/carbon rocking-chair cells that need to be charged up to a voltage higher than 4.3 V. Many electrolyte compositions have been tested for their ability to resist to high voltages on Li 1+ xMn 2O 4 electrodes and their ability to maintain high ionic conductivity in a wide temperature range. This survey allowed us to select new electrolyte compositions in the system dimethyl carbonate (DMC) + ethylene carbonate (EC) + lithium hexafluorophosphate (LiPF 6) that are kinetically stable up to almost 5 V versus lithium at 55 °C on Li 1+ xMn 2O 4 electrodes. Low rate potentiostatic experiments, coupled with coulombmetric measurements in the 4.25-5.1 V range, allowed to select the following compositions: (DMC + EC) (1:2) + 1 M LiPF 6 and (DMC + EC) (2:1) + 1.5 M LiPF 6 as the best. These compositions have been used in practical Li 1+ xMn 2O 4/carbon rocking-chair batteries and show better performance in terms of cycle life and self-discharge over a wider temperature range. They are compatible with rocking-chair batteries based on LiCoO 2 and LiNiO 2 as well.

First-principles analysis of phase stability in layered-layered composite cathodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Iddir, Hakim; Benedek, Roy; Voltage Fade Team

2014-03-01

The atomic order in layered-layered composites with composition xLi2MnO3 .(1-x)LiCoO2 is investigated with first-principles calculations at the GGA +U level. This material, and others in its class, are often regarded as solid solutions, however, only a minute solubility of Li2MnO3 in a LiCoO2 host is predicted. Calculations of Co-vacancy formation and migration energies in LiCoO2 are presented, to elucidate the rate of vacancy-mediated ordering in the transition-metal-layer, and thus determine whether low vacancy mobility could result in slow equilibration. The Co-vacancy formation energy can be predicted only to within a range, because of uncertainty in the chemical potentials. Predicted migration energies, however, are approximately 1 eV, small enough to be consistent with rapid ordering in the transition metal layer, and therefore separated Li2MnO3 and LiCoO2 phases. The relatively small (of the order of a few nm) Li2MnO3 domain sizes observed with TEM in some xLi2MnO3 .(1-x)LiMO2 composites may result from other factors, such as coherency strain, which perhaps block further domain coarsening in these materials. Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Lithium manganese oxide (LiMn{sub 2}O{sub 4}) nanoparticles synthesized by hydrothermal method as adsorbent of lithium recovery process from geothermal fluid of Lumpur Sidoarjo

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noerochim, Lukman, E-mail: lukman@mat-eng.its.ac.id; Sapputra, Gede Panca Ady; Widodo, Amien

2016-04-19

Lumpur Sidoarjo is one of geothermal fluid types which has a great potential as source of lithium. Adsorption method with Lithium Manganese Oxide (LiMn{sub 2}O{sub 4}) as an adsorbent has been chosen for lithium recovery process due to low production cost and environmental friendly. LiMn{sub 2}O{sub 4} was synthesized by hydrothermal method at 200 °C for 24 hrs, 48 hrs, and 72 hrs. As prepared LiMn{sub 2}O{sub 4} powder is treated by acid treatment with 0.5 M HCl solution for 24 hrs. XRD test result reveals that all of as-prepared samples are indexed as spinel structure of LiMn{sub 2}O{sub 4}more » (JCPDS card no 35-0782) with no impurity peaks detected. SEM images show that LiMn{sub 2}O{sub 4} has nanoparticles morphology with particle size around 25 nm. The highest adsorption efficiency of adsorbent is obtained by sample hydrothermal for 72 hrs with 42.76%.« less

Binder-free flexible LiMn2O4/carbon nanotube network as high power cathode for rechargeable hybrid aqueous battery

NASA Astrophysics Data System (ADS)

Zhu, Xiao; Wu, Xianwen; Doan, The Nam Long; Tian, Ye; Zhao, Hongbin; Chen, P.

2016-09-01

Highly flexible LiMn2O4/carbon nanotube (CNT) electrodes are developed and used as a high power cathode for the Rechargeable Hybrid Aqueous Battery (ReHAB). LiMn2O4 particles are entangled into CNT networks, forming a self-supported free-standing hybrid films. Such hybrid films can be used as electrodes of ARLB without using any additional binders. The binder-free LiMn2O4/CNT electrode exhibits good mechanical properties, high conductivity, and effective charge transport. High-rate capability and high cycling stability are obtained. Typically, the LiMn2O4/CNT electrode achieves a discharge capacity of 72 mAh g-1 at the large-current of 20 C (1 C = 120 mAh g-1), and exhibits good cycling performance and high reversibility: Coulombic efficiency of almost 100% over 300 charge-discharge cycles at 4 C. By reducing the weight, and improving the large-current rate capability simultaneously, the LiMn2O4/CNT electrode can highly enhance the energy/power density of ARLB and hold potential to be used in ultrathin, lightweight electronic devices.

The Dart estuary, Devon, UK: a case study of chemical dynamics and pollutant mobility

NASA Astrophysics Data System (ADS)

Schuwerack, P.-M. M.; Neal, M.; Neal, C.

2007-01-01

Water, sediments and gill and digestive gland tissues of adult common shore crab (Carcinus maenas), collected at Noss Marina, Sandquay (Britannia Royal Naval College), the Dartmouth Pier, Warfleet Cove and Sugary Cove in the Dart estuary, Devon, UK, were analysed for major, minor and trace elements in spring 2004. Total acid-available measurements analysed included the truly dissolved component and acid-available sediments. Trace metal concentrations are associated largely with particulate and micro-particulate/colloidal phases, the latter being able to pass through standard filter papers. Wide ranges of chemical concentrations were found in the water, sediments and tissues at all the locations. In the water column, 48% of the variance is linked to the sea-salt component (Cl, Na, K, Ca, Mg, B, Li and Sr) and the sediment-associated acid-available fractions are linked to Fe-rich lithogenous materials (Ba, Co, Cu, Fe, Mn, V and Zn). In the sediments, trace elements of Cd, Co, Cr, Fe, Pb, Mn, Ni and V are correlated with the sea salts and associated with the fraction of fine sediments within the total sediment. In the gills and the digestive gland tissues of crabs, high concentrations of Al, Cu and Fe are found and there are correlations between acid-available trace metals of Cu, Cr, Fe, Mn, Ni, Sr and Zn. The relationships between trace metal contaminants, their site-specific concentrations, their temporal and spatial variability and the effects of human activities, such as moorland/agriculture with historic mining and recreational activities in the lower Dart estuary, are discussed.

Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

PubMed

Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

2016-02-17

LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times.

Synthesis of lithium mangan dioxide (LiMn2O4) for lithium-ion battery cathode from various lithium sources

NASA Astrophysics Data System (ADS)

Priyono, S.; Ginting, N. R.; Humaidi, S.; Subhan, A.; Prihandoko, B.

2018-03-01

LiMn2O4 as a cathode material has been synthesized via solid state reaction. The synthesis has been done by varying lithium sources such as LiOH.H2O and Li2CO3 while MnO2 was used as Mn sources. All raw materials were mixed stoichiometrically to be the precursors of LiMn2O4. The precursors were sintered using high temperature furnace at 800 °C for 4 hours in atmospheric condition to form final product. The final products were sieved to separate the finer and smoother particles from the coarse ones. The products were characterized by X-Ray Diffractometer (XRD) to identify phases and crystal structure. The peak wave number was also determined using Fourier Transform Infra Red (FTIR) to find functional group. LiMn2O4 sheets were prepared by mixing active material with polyvinylidene fluoride (PVdF) and acetylene black (AB) in mass ratio of 85:10:5 wt.% in N,N-Dimethylacetamide (DMAc) solvents to form slurry. The slurry was then coated onto Al foil with thickness of about 0.15 mm and dried in an oven. LiMn2O4 sheet was cut into circular discs and arranged with separator, metallic lithium, and electrolyte in a coin cell. Automatic battery cycler was used to measure electrochemical performance and specific capacity of the cell. XRD analysis showed that sample synthesized with Li2CO3 has higher crystallinity and more pristine than sample synthesized with LiOH.H2O. FTIR analysis revealed that both of samples have identical functional group but sample with Li2CO3 source tend to degrade. Cyclic voltammetry data gave information that sample with LiOH.H2O source has better electrochemical performance. It showed double oxidation/reduction peaks more clearly but sample with Li2CO3 source has higher specific capacity (64.78 mAh/g) than sample with LiOH.H2O (50 mAh/g).

Stress Induced Charge-Ordering Process in LiMn 2O 4

DOE PAGES

Chen, Yan; Yu, Dunji; An, Ke

2016-07-25

In this letter we report the stress-induced Mn charge-ordering process in the LiMn 2O 4 spinel, evidenced by the lattice strain evolutions due to the Jahn–Teller effects. In situ neutron diffraction reveals the initial stage of this process at low stress, indicating the eg electron localization at the preferential Mn sites during the early phase transition as an underlying charge-ordering mechanism in the charge-frustrated LiMn 2O 4. The initial stage of this transition exhibits as a progressive lattice and charge evolution, without showing a first-order behavior.

Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruther, Rose E.; Samuthira Pandian, Amaresh; Yan, Pengfei

2017-03-21

Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD,more » TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

Electromigration in Cu(Al) and Cu(Mn) damascene lines

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Ohm, J.; Gignac, L. M.; Breslin, C. M.; Mittal, S.; Bonilla, G.; Edelstein, D.; Rosenberg, R.; Choi, S.; An, J. J.; Simon, A. H.; Angyal, M. S.; Clevenger, L.; Maniscalco, J.; Nogami, T.; Penny, C.; Kim, B. Y.

2012-05-01

The effects of impurities, Mn or Al, on interface and grain boundary electromigration (EM) in Cu damascene lines were investigated. The addition of Mn or Al solute caused a reduction in diffusivity at the Cu/dielectric cap interface and the EM activation energies for both Cu-alloys were found to increase by about 0.2 eV as compared to pure Cu. Mn mitigated and Al enhanced Cu grain boundary diffusion; however, no significant mitigation in Cu grain boundary diffusion was observed in low Mn concentration samples. The activation energies for Cu grain boundary diffusion were found to be 0.74 ± 0.05 eV and 0.77 ± 0.05 eV for 1.5 μm wide polycrystalline lines with pure Cu and Cu (0.5 at. % Mn) seeds, respectively. The effective charge number in Cu grain boundaries Z*GB was estimated from drift velocity and was found to be about -0.4. A significant enhancement in EM lifetimes for Cu(Al) or low Mn concentration bamboo-polycrystalline and near-bamboo grain structures was observed but not for polycrystalline-only alloy lines. These results indicated that the existence of bamboo grains in bamboo-polycrystalline lines played a critical role in slowing down the EM-induced void growth rate. The bamboo grains act as Cu diffusion blocking boundaries for grain boundary mass flow, thus generating a mechanical stress-induced back flow counterbalancing the EM force, which is the equality known as the "Blech short length effect."

Electrochemical performance of carbon-coated lithium manganese silicate for asymmetric hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Karthikeyan, K.; Aravindan, V.; Lee, S. B.; Jang, I. C.; Lim, H. H.; Park, G. J.; Yoshio, M.; Lee, Y. S.

Nanoscale carbon-coated Li 2MnSiO 4 powder is prepared using a conventional solid-state method and can be used as the negative electrode in a Li 2MnSiO 4/activated carbon (AC) hybrid supercapacitor. Carbon-coated Li 2MnSiO 4 material presents a well-developed orthorhombic crystal structure with a P mn2 1 space group, although there is a small impurity of MnO. The maximum specific capacitance of the Li 2MnSiO 4/AC hybrid supercapacitor is 43.2 F g -1 at 1 mA cm -2 current density. The cell delivers a specific energy as high as 54 Wh kg -1 at a specific power of 150 W kg -1 and also exhibits an excellent cycle performance with more than 99% columbic efficiency and the maintenance of 85% of its initial capacitance after 1000 cycles.

Effect of Morphology and Manganese Valence on the Voltage Fade and Capacity Retention of Li[Li 2/12Ni 3/12Mn 7/12]O 2

DOE PAGES

Verde, Michael G.; Liu, Haodong; Carroll, Kyler J.; ...

2014-10-02

We have determined the electrochemical characteristics of the high voltage, high capacity Li-ion battery cathode material Li[Li 2/12Ni 3/12Mn 7/12]O 2 prepared using three different synthesis routes: sol-gel, hydroxide co-precipitation, and carbonate co-precipitation. Each route leads to distinct morphologies and surface areas while maintaining the same crystal structures. X-ray photoelectron spectroscopy (XPS) measurements reveal differences in their surface chemistries upon cycling, which correlate with voltage fading. As expected, we observed the valence state of Mn on the surface to decrease upon lithiation, and this reduction is specifically correlated to discharging below 3.6V. Furthermore, the data shows a correlation of themore » formation of Li 2CO 3 with Mn oxidation state from the« less

Three-Dimensional Honeycomb-Structural LiAlO2-Modified LiMnPO4 Composite with Superior High Rate Capability as Li-Ion Battery Cathodes.

PubMed

Li, Junzhe; Luo, Shaohua; Ding, Xueyong; Wang, Qing; He, Ping

2018-04-04

In the efforts toward the rapidly increasing demands for high-power application, cathode materials with three-dimensional (3D) architectures have been proposed. Here, we report the construction of the 3D LiAlO 2 -LiMnPO 4 /C cathode materials for lithium-ion batteries in an innovation way. The as-prepared 3D active materials LiMnPO 4 /C and the honeycomb-like Li-ion conductor LiAlO 2 framework are used as working electrode directly without additional usage of polymeric binder. The electrochemical performance has been improved significantly due to the special designed core-shell architectures of LiMnPO 4 /C@LiAlO 2 . The 3D binder-free electrode exhibits high rate capability as well as superior cycling stability with a capability of ∼105 mAh g -1 and 98.4% capacity retention after 100 cycles at a high discharge rate of 10 C. Such synthesis method adopted in our work can be further extended to other promising candidates and would also inspire new avenues of development of 3D materials for lithium-ion batteries.

Structural transition in Mg-doped LiMn 2O 4: a comparison with other M-doped Li-Mn spinels

NASA Astrophysics Data System (ADS)

Capsoni, Doretta; Bini, Marcella; Chiodelli, Gaetano; Massarotti, Vincenzo; Mozzati, Maria Cristina; Azzoni, Carlo B.

2003-01-01

The charge distribution in the Mg-doped lithium manganese spinel Li 1.02Mg xMn 1.98- xO 4 with 0.00< x≤0.20 is discussed and compared to those pertinent to other M-doped samples (M=Ni 2+, Co 3+, Cr 3+, Al 3+ and Ga 3+). EPR spectra, low temperature X-ray diffraction and conductivity data are related to the cooperative Jahn-Teller (J-T) transition occurring at about 280 K in the undoped sample. The sensitivity of the cationic sublattice in displaying electronic and magnetic changes after substitution is remarked. The inhibition of the J-T transition is related to the ratio r=|Mn 4+|/|Mn 3+| as deduced from the charge distribution model [Li 1- xt+Mg xt2+] tetr[Li y+ xt+Mg xo2+Mn 1-3 y-2 x3+Mn 1+2 y+ x4+] octa where x= xo+ xt. For y=0.02 and x=0.02, a value r=1.177 is obtained, very close to rlim=1.18, the limit value beyond which the transition is inhibited.

Three-Dimensional LiMnPO4·Li3V2(PO4)3/C Nanocomposite as a Bicontinuous Cathode for High-Rate and Long-Life Lithium-Ion Batteries.

PubMed

Luo, Yanzhu; Xu, Xu; Zhang, Yuxiang; Pi, Yuqiang; Yan, Mengyu; Wei, Qiulong; Tian, Xiaocong; Mai, Liqiang

2015-08-12

Olivine-type LiMnPO4 has been extensively studied as a high-energy density cathode material for lithium-ion batteries. To improve both the ionic and electronic conductivities of LiMnPO4, a series of carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposites are synthesized by a facile sol-gel method combined with the conventional solid-state method. The optimized composite presents a three-dimensional hierarchical structure with active nanoparticles well-embedded in a conductive carbon matrix. The combination of the nanoscale carbon coating and the microscale carbon network could provide a more active site for electrochemical reaction, as well as a highly conductive network for both electron and lithium-ion transportation. When cycled at 20 C, an initial specific capacity of 103 mA h g(-1) can be obtained and the capacity retention reaches 68% after 3000 cycles, corresponding to a capacity fading of 0.013% per cycle. The stable capacity and excellent rate capability make this carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposite a promising cathode for lithium-ion batteries.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Bohang; Li, Wangda; Yan, Pengfei

A facile synthesis method was developed to prepare xLi 2MnO 3·(1-x)LiNi 0.7Co 0.15Mn 0.15O 2 (x = 0, 0.03, 0.07, 0.10, 0.20, and 0.30 as molar ratio) cathode materials, combining the advantages of high specific capacity from Ni-rich layered phase and surface chemical stability from Li-rich layered phase. X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM) and electrochemical charge/discharge performance confirm the formation of a Li-rich layered phase with C2/m symmetry. Most importantly, high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) reveals a spatial relationship that Li-rich nano-domain islands are integrated into a conventional Ni-rich layered matrix (Rmore » $$\\bar{3}$$m). This is the first time that Li-rich phase has been directly observed inside a particle at the nano-scale, when the overall composition of layered compounds (Li 1+δNi xMn yM 1-x-y-δO 2, M refers to transition metal elements) is Ni-rich (x > 0.5) rather than Mn-rich (y > 0.5). Remarkably, xLi 2MnO 3·(1-x)LiNi 0.7Co 0.15Mn 0.15O 2 cathode with optimized x value shows superior electrochemical performance at C/3, i.e., 170 mA h g -1 with 90.3 % of capacity retention after 400 cycles at 25 °C and 164 mA h g -1 with 81.3 % capacity retention after 200 cycles at 55 °C.« less

Thermoelectric properties of a Mn substituted synthetic tetrahedrite.

PubMed

Chetty, Raju; D S, Prem Kumar; Rogl, Gerda; Rogl, Peter; Bauer, Ernst; Michor, Herwig; Suwas, Satyam; Puchegger, Stephan; Giester, Gerald; Mallik, Ramesh Chandra

2015-01-21

Tetrahedrite compounds Cu(12-x)Mn(x)Sb4S13 (0 ≤x≤ 1.8) were prepared by solid state synthesis. A detailed crystal structure analysis of Cu10.6Mn1.4Sb4S13 was performed by single crystal X-ray diffraction (XRD) at 100, 200 and 300 K confirming the noncentrosymmetric structure (space group I4[combining macron]3m) of a tetrahedrite. The large atomic displacement parameter of the Cu2 atoms was described by splitting the 12e site into a partially and randomly occupied 24g site (Cu22) in addition to the regular 12e site (Cu21), suggesting a mix of dynamic and static off-plane Cu2 atom disorder. Rietveld powder XRD pattern and electron probe microanalysis revealed that all the Mn substituted samples showed a single tetrahedrite phase. The electrical resistivity increased with increasing Mn due to substitution of Mn(2+) at the Cu(1+) site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. Even though the thermal conductivity decreased as a function of increasing Mn, the thermoelectric figure of merit ZT decreased, because the decrease of the power factor is stronger than the decrease of the thermal conductivity. The maximum ZT = 0.76 at 623 K is obtained for Cu12Sb4S13. The coefficient of thermal expansion 13.5 ± 0.1 × 10(-6) K(-1) is obtained in the temperature range from 460 K to 670 K for Cu10.2Mn1.8Sb4S13. The Debye temperature, Θ(D) = 244 K for Cu10.2Mn1.8Sb4S13, was estimated from an evaluation of the elastic properties. The effective paramagnetic moment 7.45 μB/f.u. for Cu10.2Mn1.8Sb4S13 is fairly consistent with a high spin 3d(5) ground state of Mn.

Solid state 31phosphorus nuclear magnetic resonance of iron-, manganese-, and copper-containing synthetic hydroxyapatites

NASA Technical Reports Server (NTRS)

Sutter, B.; Taylor, R. E.; Hossner, L. R.; Ming, D. W.

2002-01-01

The incorporation of micronutrients into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in the National Aeronautics and Space Administration's (NASA's) Advanced Life Support (ALS) program for Lunar or Martian outposts. Solid state 31P nuclear magnetic resonance (NMR) was utilized to examine the paramagnetic effects of Fe3+, Mn2+, and Cu2+ to determine if they were incorporated into the SHA structure. Separate Fe3+, Mn2+, and Cu2+ containing SHA materials along with a transition metal free SHA (pure-SHA) were synthesized using a precipitation method. The proximity (<1 nm) of the transition metals to the 31P nuclei of SHA were apparent when comparing the integrated 31P signal intensities of the pure-SHA (87 arbitrary units g-1) with the Fe-, Mn-, and Cu-SHA materials (37-71 arbitrary units g-1). The lower integrated 31P signal intensities of the Fe-, Mn-, and Cu-SHA materials relative to the pure-SHA suggested that Fe3+, Mn2+, and Cu2+ were incorporated in the SHA structure. Further support for Fe3+, Mn2+, and Cu2+ incorporation was demonstrated by the reduced spin-lattice relaxation constants of the Fe-, Mn-, and Cu-SHA materials (T'=0.075-0.434s) relative to pure-SHA (T1=58.4s). Inversion recovery spectra indicated that Fe3+, Mn2+, and Cu2+ were not homogeneously distributed about the 31P nuclei in the SHA structure. Extraction with diethylene-triamine-penta-acetic acid (DTPA) suggested that between 50 and 80% of the total starting metal concentrations were incorporated in the SHA structure. Iron-, Mn-, and Cu-containing SHA are potential slow release sources of Fe, Mn, and Cu in the ALS cropping system.

Mitigation of chromium poisoning of cathodes in solid oxide fuel cells employing CuMn1.8O4 spinel coating on metallic interconnect

NASA Astrophysics Data System (ADS)

Wang, Ruofan; Sun, Zhihao; Pal, Uday B.; Gopalan, Srikanth; Basu, Soumendra N.

2018-02-01

Chromium poisoning is one of the major reasons for cathode performance degradation in solid oxide fuel cells (SOFCs). To mitigate the effect of Cr-poisoning, a protective coating on the surface of interconnect for suppressing Cr vaporization is necessary. Among the various coating materials, Cu-Mn spinel coating is considered to be a potential candidate due to their good thermal compatibility, high stability and good electronic conductivity at high temperature. In this study, Crofer 22 H meshes with no protective coating, those with commercial CuMn2O4 spinel coating and the ones with lab-developed CuMn1.8O4 spinel coating were investigated. The lab-developed CuMn1.8O4 spinel coating were deposited on Crofer 22 H mesh by electrophoretic deposition and densified by a reduction and re-oxidation process. With these different Crofer 22 H meshes (bare, CuMn2O4-coated, and CuMn1.8O4-coated), anode-supported SOFCs with Sr-doped LaMnO3-based cathode were electrochemically tested at 800 °C for total durations of up to 288 h. Comparing the mitigating effects of the two types of Cu-Mn spinel coatings on Cr-poisoning, it was found that the performance of the denser lab-developed CuMn1.8O4 spinel coating was distinctly better, showing no degradation in the cell electrochemical performance and significantly less Cr deposition near the cathode/electrolyte interface after the test.

Effect of Mn in Li3V2-xMnx(PO4)3 as High Capacity Cathodes for Lithium Batteries.

PubMed

Park, Jae-Sang; Kim, Jongsoon; Park, Woon Bae; Sun, Yang-Kook; Myung, Seung-Taek

2017-11-22

Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) cathode materials, which allow extraction of 3 mol of Li from the formula unit, were investigated to achieve a high energy density utilizing multielectron reactions, activated by the V 3+/5+ redox reaction. Structural investigation demonstrates that V 3+ was replaced by equivalent Mn 3+ , as confirmed by Rietveld refinement of the X-ray diffraction data and X-ray absorption near edge spectroscopy. The substitution simultaneously lowered the band gap energy from 3.4 to 3.2 eV, according to a density functional theory calculation. In addition to the effect of Mn doping, surface carbonization of Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) dramatically increased the electric conductivity up to 10 -3 S cm -1 . As a result, the carbon-coated Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0.05) delivered a high discharge (reduction) capacity of approximately 180 mAh g -1 at a current of 20 mA g -1 (0.1 C rate) with excellent retention, delivering approximately 163 mAh g -1 at the 200th cycle. Even at 50 C (10 A g -1 ), the electrode afforded a discharge capacity of 68 mAh g -1 and delivered approximately 104 mAh g -1 (1 C) at -10 °C with the help of Mn doping and carbon coating. The synergetic effects such as a lowered band gap energy by Mn doping and high electric conductivity associated with carbon coating are responsible for the superior electrode performances, including thermal properties with extremely low exothermic heat generation (<0.4 J g -1 for Li 0.02 V 1.95 Mn 0.05 (PO 4 ) 3 ), which is compatible with the layered high energy density of LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 materials.

Single- and double-ion type cross-linked polysiloxane solid electrolytes for lithium cells

NASA Astrophysics Data System (ADS)

Tsutsumi, Hiromori; Yamamoto, Masahiro; Morita, Masayuki; Matsuda, Yoshiharu; Nakamura, Takashi; Asai, Hiroyuki

Polymeric solid electrolytes, that have poly(dimethylsiloxane) (PMS) backbone and cross-linked network, were applied to a rechargeable lithium battery system. Single- (PMS-Li) and double-ion type (PMS-LiClO 4) electrolytes were prepared from the same prepolymers. Lithium electrode in the both electrolytes showed reversible stripping and deposition of lithium. Intercalation and deintercalation processes of lithium ion between lithium-manganese composite oxide (Li xMnO 2) electrode and the electrolytes were also confirmed by cyclic voltammetry, however, peak current decreased with several cycles in both cases. The model cell, Li/PMS-Li/Li xMnO 2 cell had 1.4 mA h g -1 (per 1 g of active material, current density: 3.77 μA cm -2), and the Li/PMS-LiClO 4/Li xMnO 2 cell had 1.6 mA h g -1 (current density: 75.3 μA cm -2).

Early stage sustainability evaluation of new, nanoscale cathode materials for Li-ion batteries.

PubMed

Hischier, Roland; Kwon, Nam Hee; Brog, Jean-Pierre; Fromm, Katharina M

2018-05-07

We present results of early stage sustainability evaluation of two development strategies for new, nano-scale cathode materials for Li-ion batteries: (i) a new production pathway of existing material (LiCoO2), and (ii) a new nanomaterial (LiMnPO4). Nano-LiCoO2 was synthesized via a single source precursor route at lower temperature with a shorter reaction time, resulting in a smaller grain size and, thereby, a better diffusivity for Li-ions. Nano-LiMnPO4 was synthesized via a wet chemical method. The sustainability potential of these materials has then been investigated (at the laboratory and pilot production scales). The results show that the environmental impact of nano-LiMnPO4 is lower compared to the other examined nanomaterial by several factors, and this regardless of the indicator for the comparison. In contrast to commercial cathode materials, this new material shows, particularly on an energy and capacity basis, results in the same order of magnitude as those of lithium manganese oxide (LiMn2O4), and only slightly higher values than those for lithium iron phosphate (LiFePO4); values that are clearly lower than those for high-temperature LiCoO2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward a stable solid-electrolyte-interfaces on nickel-rich cathodes: LiPO2F2 salt-type additive and its working mechanism for LiNi0.5Mn0.25Co0.25O2 cathodes

NASA Astrophysics Data System (ADS)

Zhao, Weimin; Zheng, Guorui; Lin, Min; Zhao, Wengao; Li, Dongjiang; Guan, Xiaoyun; Ji, Yajuan; Ortiz, Gregorio F.; Yang, Yong

2018-03-01

Although the LiNi0.5Mn0.25Co0.25O2 holds the merits of high theoretical capacities and a relatively high operating voltage, the battery performance suffers from the severe cycling decay due to the unstable solid electrolyte interface on the cathode. Herein, we present LiPO2F2 as a salt-type electrolyte additive to enhance the cycling stability of large-size crystallite LiNi0.5Mn0.25Co0.25O2 cathodes. Results demonstrate that 1 wt% LiPO2F2 can significantly improve not only the initial coulombic efficiency by 3%, but also the cycling stability and rate capability at 25 °C. Furthermore, the discharge capacity of LiNi0.5Mn0.25Co0.25O2 cathodes still maintain 156 mAh g-1 after 100 cycles even when the temperature increases to 55 °C. In-depth experimental characterization and theoretical calculation indicate that a new stable and thin (e.g. 15-20 nm) film formed on the surface of the cathodes, with composition of LiPO2F2, LiF, etc., which significantly reduces charge transfer impedance of the electrodes, and therefore significantly improves the cycling and rate performance of LiNi0.5Mn0.25Co0.25O2.

Manganese oxide composite electrodes for lithium batteries

DOEpatents

Thackeray, Michael M.; Johnson, Christopher S.; Li, Naichao

2007-12-04

An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0

Synthesis and Electrochemical Properties Characterization of SnO2-coated LiNi1/3Co1/3Mn1/3O2 Cathode Material for Lithium Ion Batteries

DTIC Science & Technology

2009-01-01

Synthesis and electrochemical properties characterization of SnO2-coated LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries Ping Yang...electrochemical properties characterization of SnO2-coated LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries 5a. CONTRACT NUMBER 5b. GRANT NUMBER...electrochemical reaction. References 1. N Yabuuchi, T Ohzuku, “Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium - ion batteries ”, J

CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions

PubMed Central

Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

2017-01-01

A conservative CO2-Methanol (CH3OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO2 by aqueous hydrogenation for industry-useful CH3OH and to convert aqueous CH3OH solution by dehydrogenation for the clean energy of hydrogen (H2), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu+]-high CuMnOS led to a CH3OH yield of 21.1 mmol·g−1catal.·h−1 in the CuMnOS-CO2-H2O system and the other [Cu+]-low one had a H2 yield of 7.65 mmol·g−1catal.·h−1 in the CuMnOS-CH3OH-H2O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu+ and Cu2+. The CO2-hydrogenated CH3OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application. PMID:28117456

CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions

NASA Astrophysics Data System (ADS)

Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

2017-01-01

A conservative CO2-Methanol (CH3OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO2 by aqueous hydrogenation for industry-useful CH3OH and to convert aqueous CH3OH solution by dehydrogenation for the clean energy of hydrogen (H2), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu+]-high CuMnOS led to a CH3OH yield of 21.1 mmol·g-1catal.·h-1 in the CuMnOS-CO2-H2O system and the other [Cu+]-low one had a H2 yield of 7.65 mmol·g-1catal.·h-1 in the CuMnOS-CH3OH-H2O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu+ and Cu2+. The CO2-hydrogenated CH3OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application.

CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions.

PubMed

Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

2017-01-24

A conservative CO 2 -Methanol (CH 3 OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO 2 by aqueous hydrogenation for industry-useful CH 3 OH and to convert aqueous CH 3 OH solution by dehydrogenation for the clean energy of hydrogen (H 2 ), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu + ]-high CuMnOS led to a CH 3 OH yield of 21.1 mmol·g -1 catal.·h -1 in the CuMnOS-CO 2 -H 2 O system and the other [Cu + ]-low one had a H 2 yield of 7.65 mmol·g -1 catal.·h -1 in the CuMnOS-CH 3 OH-H 2 O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu + and Cu 2+ . The CO 2 -hydrogenated CH 3 OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application.

Phases of LiMn1.84V0.06Ti0.1O4 cathode material

NASA Astrophysics Data System (ADS)

Zainol, N. H.; Kamarulzaman, N.; Osman, Z.; Fadzil, A. F. M.; Yahya, N. F.

2017-09-01

In this work, LiMn1.84V0.06Ti0.1O4 was prepared via a combustion method using citric acid as a reductant. The precursor obtained was annealed at 700 °C for 24h in a furnace. The thermal profile of the precursor was obtained by simultaneous thermogravimetric analysis (STA). The observed material was characterized by X-ray Diffraction (XRD) and found to be pure and single-phase of cubic structure. The electrochemical performance of LiMn1.84V0.06Ti0.1O4 cathode material was studied by applying a constant current of 1.0 mA at a voltage range of 4.2 to 2.5 V. The specific capacity of LiMn1.84V0.06Ti0.1O4 cathode material at the 1st cycle shows the value of 95mAh/g which is less than the specific capacity of LiMn2O4, which is 117 mAh/g.

Lithium Nitride Synthesized by in situ Lithium Deposition and Ion Implantation for Boron Neutron Capture Therapy

NASA Astrophysics Data System (ADS)

Ishitama, Shintaro; Baba, Yuji; Fujii, Ryo; Nakamura, Masaru; Imahori, Yoshio

Li3N synthesis on Li deposition layer was conducted without H2O and O2 by in situ lithium deposition in high vacuum chamber of 10-6 Pa and ion implantation techniques and the thermo-chemical stability of the Li3N/Li/Cu tri-layered target for Boron Neutron Capture Therapy (BNCT) under laser heating and air exposure was characterized by X-ray photoelectron spectroscopy (XPS). Following conclusions were derived; (1) Li3N/Li/Cu tri-layered target with very low oxide and carbon contamination was synthesized by in situ lithium vacuum deposition and N2+ ion implantation without H2O and O2 additions, (2) The starting temperature of evaporation of Li3N/Li/Cu tri-layered target increased by 120K compared to that of the Li/Cu target and (3) Remarkable oxidation and carbon contamination were observed on the surface of Li3N/Li/Cu after air exposure and these contaminated compositions was not removed by Ar+ heavy sputtering.

Effect of chemical treatment on the electrochemical properties of Li1.2NixMn0.8-xO2 (x = 0.2 and 0.25) in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei

2018-02-01

The effect of chemical treatment using (NH4)2SO4 on the electrochemical properties of Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.25Mn0.55O2 was investigated. The treatment was effective in improving the Coulombic efficiency and discharge capacity of a Li1.2Ni0.2Mn0.6O2 cathode, but treatment with too much (NH4)2SO4 degraded the cathode's electrochemical performance. The effect of (NH4)2SO4 treatment on the charge-discharge reaction mechanism of Li1.2Ni0.2Mn0.6O2 was investigated by evaluating reaction potential, particle configuration, and oxidation state of transition metal. The experimental results indicated that the changes in the electrochemical performance of the treated cathodes were attributed to the changes in the surface state and of the element contributing to the redox reaction. Treatment with an appropriate amount of (NH4)2SO4 also improved the electrochemical performance of the high-nickel-content lithium-rich layer-structured cathode material Li1.2Ni0.25Mn0.55O2.

The excellent performance of nest-like oxygen-deficient Cu1.5Mn1.5O4 applied in activated carbon air-cathode microbial fuel cell.

PubMed

Wang, Junjie; Tian, Pei; Li, Kexun; Ge, Baochao; Liu, Di; Liu, Yi; Yang, Tingting; Ren, Rong

2016-12-01

This study investigated the performance of nano spinel nest-like oxygen-deficient Cu 1.5 Mn 1.5 O 4 doping activated carbon (AC) as air cathode in microbial fuel cell (MFC). The Cu 1.5 Mn 1.5 O 4 was synthesized via hydrothermal method and subsequent annealed. The maximum power density (MPD) of MFC with oxygen-deficient Cu 1.5 Mn 1.5 O 4 modified cathode was 1928±18mWm -2 , which was 1.53 times higher than the bare cathode. The electrochemical studies showed that Cu 1.5 Mn 1.5 O 4 doping AC exhibited higher kinetic activity and lower resistance. The mechanism of oxygen reduction for the catalyst was a four electron pathway. The oxygen deficient of Cu 1.5 Mn 1.5 O 4 played an important role in catalytic activity. So Cu 1.5 Mn 1.5 O 4 would be an excellent promising catalyst for ORR in MFC. Copyright © 2016 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp; Nakamura, Ayumi; Miura, Akira

A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4}more » all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.« less

Effect of CeLa addition on the microstructures and mechanical properties of Al-Cu-Mn-Mg-Fe alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Jiandi

Development of high strength lithium battery shell alloy is highly desired for new energy automobile industry. The microstructures and mechanical properties of Al-Cu-Mn-Mg-Fe alloy with different CeLa additions were investigated through optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rietveld refinement and tensile testing. Experimental results indicate that Al{sub 8}Cu{sub 4}Ce and Al{sub 6}Cu{sub 6}La phases formed due to CeLa addition. Addition of 0.25 wt.% CeLa could promote the formation of denser precipitation of Al{sub 20}Cu{sub 2}Mn{sub 3} and Al{sub 6}(Mn, Fe) phases, which improved the mechanical properties of the alloy at room temperature.more » However, up to 0.50 wt.% CeLa addition could promote the formation of coarse Al{sub 8}Cu{sub 4}Ce phase, Al{sub 6}Cu{sub 6}La phase and Al{sub 6}(Mn, Fe) phase, which resulted in weakened mechanical properties. - Highlights: •Al-Cu-Mn-Mg-Fe alloys with different CeLa addition were fabricated through casting and rolling. •Al{sub 8}Cu{sub 4}Ce and Al{sub 6}Cu{sub 6}La phases formed after CeLa addition. •Addition of 0.25 wt.% CeLa promoted formation of denser precipitates of Al{sub 20}Cu{sub 2}Mn{sub 3} and Al{sub 6}(Mn, Fe). •Mechanical properties of the alloy was improved after 0.25 wt.% CeLa addition.« less

Anode materials for lithium ion batteries

DOEpatents

Abouimrane, Ali; Amine, Khalil

2015-06-09

A composite material has general Formula (1-x)J-(x)Q wherein: J is a metal carbon alloy of formula Sn.sub.zSi.sub.z'Met.sub.wMet'.sub.w'C.sub.t; Q is a metal oxide of formula A.sub..gamma.M.sub..alpha.M'.sub..alpha.'O.sub..beta.; A is Li, Na, or K; M, M', Met, and Met' are individually Ge, Mo, Al, Ga, As, Sb, Te, Ti, Ta, Zr, Ca, Mg, Sr, Ba, Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Rt, Ru or Cd; 0

First-principles study on alkali-metal effect of Li, Na, and K in CuInSe2 and CuGaSe2

NASA Astrophysics Data System (ADS)

Maeda, Tsuyoshi; Kawabata, Atsuhito; Wada, Takahiro

2015-08-01

The substitution energies and migration energies of the alkali metal atoms of Li, Na, and K in CuInSe2 (CIS) and CuGaSe2 (CGS) were investigated by first-principles calculations. The substitution energies of Li, Na, and K atoms in CIS and CGS were calculated for two different cationic atom positions of Cu and In/Ga in the chalcopyrite unit cell. In CIS and CGS, the substitution energies of NaCu are much lower than those of NaIn and NaGa. The substitution energies of the LiCu atoms in CIS and CGS are lower than those of NaCu, while the substitution energies of KCu atoms in CIS and CGS are much higher than those of NaCu. Therefore, it is difficult to form KCu in CIS and CGS. The migration energies of Li, Na, and K atoms in CIS and CGS are obtained by a combination of the linear and quadratic synchronous transit (LST/QST) methods and the nudged elastic band (NEB) method. The theoretical migration energies of a Na atom at the Cu site to the nearest Cu vacancy (NaCu → VCu) in CIS and CGS are much lower than those of (CuCu → VCu) in CIS and CGS. The mechanism underlying the alkali metal effect of Li, Na, and K in the CIGS film during the post-deposition treatment of LiF, NaF, and KF is discussed on the basis of the calculated substitution and migration energies.

Effect of boric acid on the properties of Li{sub 2}MnO{sub 3}·LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} composite cathode powders prepared by large-scale spray pyrolysis with droplet classifier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Young Jun; Choi, Seung Ho; Sim, Chul Min

2012-12-15

Graphical abstract: Display Omitted Highlights: ► Spherical shape Li{sub 2}MnO{sub 3}·LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} composite cathode powders are prepared by large-scale spray pyrolysis with droplet classifier. ► Boric acid improves the morphological and electrochemical properties of the composite cathode powders. ► The discharge capacity of the composite cathode powders decreases from 217 to 196 mAh g{sup −1} by the 30th cycle. -- Abstract: Spherically shaped 0.3Li{sub 2}MnO{sub 3}·0.7LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} composite cathode powders with filled morphology and narrow size distribution are prepared by large-scale spray pyrolysis. A droplet classification reduces the standard deviation of the size distribution of themore » composite cathode powders. Addition of boric acid improves the morphological properties of the product powders by forming a lithium borate glass material with low melting temperature. The optimum amount of boric acid dissolved in the spray solution is 0.8 wt% of the composite powders. The powders prepared from the spray solution with 0.8 wt% boric acid have a mixed layered crystal structure comprising Li{sub 2}MnO{sub 3} and LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} phases, thus forming a composite compound. The initial charge and discharge capacities of the composite cathode powders prepared from the 0.8 wt% boric acid spray solution are 297 and 217 mAh g{sup −1}, respectively. The discharge capacity of the powders decreases from 217 to 196 mAh g{sup −1} by the 30th cycle, in which the capacity retention is 90%.« less

Biosorption of copper, nickel and manganese using non-living biomass of marine alga, Ulva lactuca.

PubMed

Omar, Hanan Hafez

2008-04-01

The adsorption of Cu2+, Ni2+ and Mn2+ onto the marine algal biomass of Ulva lactuca was investigated in single and multimetal solutions. This study was intended to determine the role of different pH values (2-8) on the biosorption of metals at different concentrations (10, 20 and 30 mg L(-1)). The biosorption capacity of Cu2+, Ni2+ and Mn2+ for 10 mg L(-1) was the same as 20 and 30 mg L(-1), increase with increasing pH up to pH 5.0 and then decreased, in single and multimetal solutions. The optimum pH value was observed in the pH range 4-5 for Cu2+ and pH 5-6 for Ni2+ and Mn2+. The maximum biosorption capacities of tested alga for Cu2+, Ni2+ and Mn2+ were 92, 80 and 75%, respectively in single metal solution at 10 mg L(-1) and pH 5.0. At a further increase of pH (8.0) the biosorption process for Cu2+, Ni2+ and Mn2+ (75, 69 and 63%, respectively at 10 mg L(-1)) was decreased. The minimum biosorptions were 60, 49 and 44% for Cu2+, Ni2+ and Mn2+, respectively in single metal solution at 10 mg L(-1) and pH 2.0. In the multimetal solution, algal biomass exhibited the maximum and the minimum biosorption capacity at different pH values the same as in single metal solution. The inhibitory role of other ions on sorption process can be well observed in multimetal mixture, where biosorption capacity of Cu2+, Ni2+ and Mn2+ were significantly decreased in the multimetal solutions. The maximum biosorption was recorded for Cu2+ (83%) in solution of Cu2+ + Mn2+, Mn2+ (67%) in solution of Ni2 + Mn2+ and for Ni2+ (74%) in solution of Ni2+ + Mn2+ at the concentration 10 mg L(-1) and pH 5.0. The observed reduction in the biosorption of Cu2+, Ni2+ and Mn2+ (65, 57 and 52%, respectively at 10 mg L(-1) and pH 5.0) was more pronounced in the multimetal solution of Cu2 + Ni2+ + Mn2+ as compared with single metal solution. The results demonstrated that the affinity of the tested alga for sorption of the investigated metal ions in single and multimetal solutions runs in the order Cu2+ > Ni2+ > Mn2+. Biosorption equilibrium was established by the Langmuir and Freundlich isotherm models. According to the analyses conducted, the biosorption of Cu2+, Ni2+ and Mn2+ to Ulva lactuca was more consistent with Freundlich isotherm.

Chemical obtaining of LiMO2 and LiM2O4 (M=Co, Mn) oxides, for cathodic applications in Li-ion batteries

NASA Astrophysics Data System (ADS)

Y Neira-Guio, A.; Gómez Cuaspud, J. A.; López, E. Vera; Pineda Triana, Y.

2017-12-01

This paper describes the synthesis and characterization of two spinel and olivine-type multicomponent oxides based on LiMO2 and LiM2O4 systems (M=Co and Mn), which represent the current state of the art in the development of cathodes for Li-ion batteries. A simple combustion synthesis process was employed to obtain the nanometric oxides in powder form (crystal sizes around 5-8nm), with a number of improved surface characteristics. The characterization by X-Ray Diffraction (XRD), Scanning and Transmission Electron Microscopy (SEM, TEM) and X-Ray Fluorescence (XRF), allowed to evaluate the morphology and the stoichiometric compositions of solids, obtaining a concordant pure crystalline phase of LiCoO2 and LiMn2O4 oxides identified in a rhombohedral and cubic phase with punctual group R-3m (1 6 6) and Fm-3m (2 2 5) respectively. The electrical characterization of materials developed by impedance spectroscopy solid state, allowed to determine a p-type semiconducting behaviour with conductivity values of 6.2×10-3 and 2.7×10-7 S for LiCoO2 and LiMn2O4 systems, consistent with the state of the art for such materials.

Crystal engineering in 3D: Converting nanoscale lamellar manganese oxide to cubic spinel while affixed to a carbon architecture

DOE PAGES

Donakowski, Martin D.; Wallace, Jean M.; Sassin, Megan B.; ...

2016-06-17

Here, by applying differential pair distribution function (DPDF) analyses to the energy–storage relevant MnOx/carbon system— but in a 3D architectural rather than powder–composite configuration—we can remove contributions of the carbon nanofoam paper scaffold and quantify the multiphasic oxide speciation as the nanoscale, disordered MnOx grafted to the carbon walls (MnOx@CNF) structurally rearranges in situ from birnessite AMnOx (A = Na +; Li +) to tetragonal Mn 3O 4 to spinel LiMn 2O 4. The first reaction step involves topotactic exchange of interlayer Na + by Li + in solution followed by thermal treatments to crystal engineer the –10–nm–thick 2D layeredmore » oxide throughout the macroscale nanofoam paper into a spinel phase. The oxide remains affixed to the walls of the nanofoam throughout the phase transformations. The DPDF fits are improved by retention of one plane of birnessite–like oxide after conversion to spinel. We support the DPDF–derived assignments by X–ray photoelectron spectroscopy and Raman spectroscopy, the latter of which tracks how crystal engineering the oxide affects the disorder of the carbon substrate. We further benchmark MnOx@CNF with nonaqueous electrochemical measurements versus lithium as the oxide converts from X–ray–amorphous birnessite to interlayer-registered LiMnOx to spinel. The lamellar AMnOx displays pseudocapacitive electrochemical behavior, with a doubling of specific capacitance for the interlayer–registered LiMnOx, while the spinel LiMn 2O 4@CNF displays a faradaic electrochemical response characteristic of Li–ion insertion. Our results highlight the need for holistic understanding when crystal engineering an (atomistic) charge–storing phase within the (architectural) structure of practical electrodes.« less

Spatial Variations and Sources of Trace Elements in Recent Snow from Glaciers at the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Huang, J.; Li, Y.; Li, Z.; Cozzi, G.; Turetta, C.; Barbante, C.; Xiong, L.

2017-12-01

Various trace element (TEs) could be long-range transported through the atmosphere and deposited onto the snow surface. Recently, with the development of economy of China and the surrounding countries, TEs such as Pb, Cd, Mo and Sb in several glaciers from the Tibetan Plateau (TP) have been gradually affected by anthropogenic activities. This study presents the acid leached concentrations of TEs (e.g., Al, As, Ba, Co, Cr, Cs, Cu, Fe, Li, Mn, Mo, Pb, Rb, Sb, Sr, Ti, Tl, U, V) and dust content sampled from Qiumianleike (QMLK), Meikuang (MK), Yuzhufeng (YZF), Xiaodongkemadi (XDKMD), Gurenhekou (GRHK) glaciers on the TP from April to May of 2013. The different concentrations of TEs in the surface snow and snow pit samples over the five glaciers show that TEs were influenced both by surrounding environment of glaciers and seasonal variations of atmospheric impurity loading. Comparison of TEs concentrations with data of other sites, elevated concentrations of As, Cu, Mo, Pb and Sb were observed in glaciers of TP, showing significant atmospheric TEs pollution. Enrichment factor(EF) analysis indicates that Rb, V, U, Cr, Ba, Cs, Li, As, Co, Mn, Tl, Sr and Cu mainly originated from crustal dust, while anthropogenic inputs such as nonferrous metals melting, coal combustion and traffic emission made an important contribution to the Mo, Pb and Sb. Evidences from air mass back trajectories show the air masses arrived at QMLK mostly came from the Taklimakan desert, the TEs from the Taklimakan desert and the western TP could be transported to the MK and YZF glaciers . The air masses derived from the western TP and the southwestern TP affected the environment of the XDKMD and GRHK glaciers. Futhermore, the air masses passed through some big cities with developed industry and large population such as Urumqi, Bishkek, Dushanbe and some countries such as Pakistan and India could also bring pollutants to the studied glaciers.

First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces

DOE PAGES

Leung, Kevin

2016-12-10

The density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn–O bonds forming mobile OH – surface groups; and chemicalmore » reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. Our findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Improved Cycling Stability and Fast Charge-Discharge Performance of Cobalt-Free Lithium-Rich Oxides by Magnesium-Doping.

PubMed

Yi, Ting-Feng; Li, Yan-Mei; Yang, Shuang-Yuan; Zhu, Yan-Rong; Xie, Ying

2016-11-30

Layered Li-rich, Co-free, and Mn-based cathode material, Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (0 ≤ x ≤ 0.05), was successfully synthesized by a coprecipitation method. All prepared samples have typical Li-rich layered structure, and Mg has been doped in the Li 1.17 Ni 0.25 Mn 0.58 O 2 material successfully and homogeneously. The morphology and the grain size of all material are not changed by Mg doping. All materials have a estimated size of about 200 nm with a narrow particle size distribution. The electrochemical property results show that Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.01 and 0.02) electrodes exhibit higher rate capability than that of the pristine one. Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.02) indicates the largest reversible capacity of 148.3 mAh g -1 and best cycling stability (capacity retention of 95.1%) after 100 cycles at 2C charge-discharge rate. Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.02) also shows the largest discharge capacity of 149.2 mAh g -1 discharged at 1C rate at elevated temperature (55 °C) after 50 cycles. The improved electrochemical performances may be attributed to the decreased polarization, reduced charge transfer resistance, enhanced the reversibility of Li + ion insertion/extraction, and increased lithium ion diffusion coefficient. This promising result gives a new understanding for designing the structure and improving the electrochemical performance of Li-rich cathode materials for the next-generation lithium-ion battery with high rate cycling performance.

Influence of internal electric fields on bonding and properties of impurities in insulators: Mn2+ in LiBaF3 and normal perovskites

NASA Astrophysics Data System (ADS)

Trueba, A.; García-Lastra, J. M.; Barriuso, M. T.; Aramburu, J. A.; Moreno, M.

2008-08-01

Although in LiBaF3:Mn2+ the impurity replaces Li+ thus forming octahedral MnF64- units the experimental hyperfine and anisotropic superhyperfine constants and the energies of d-d optical transitions do not fit into the pattern observed for Mn2+ -doped normal perovskite lattices. Seeking to look into this relevant issue first-principles calculations in the framework of the density-functional theory have been carried out for MnF64- complexes embedded in both KMgF3 and LiBaF3 host lattices which display normal and inverted perovskite structures respectively. The present calculations lead to a value of the equilibrium Mn2+-F- distance, RI , which is the same for both host lattices within 0.015Å . Despite this fact and in agreement with experimental data the calculated values of both the anisotropic superhyperfine constant, Ap , and the cubic-field splitting parameter, 10Dq, for LiBaF3:Mn2+ are found to be higher than those for KMgF3:Mn2+ while Racah parameters are a bit higher for the latter case. All these results, and also the 3% reduction undergone by the hyperfine constant on passing from KMgF3:Mn2+ to LiBaF3:Mn2+ are shown to be connected with a parallel increase in the covalency. These surprising results, which cannot be ascribed to a different RI value, are shown to arise from the internal electric field, ER , due to all lattice ions lying outside the MnF64- complex. Although, according to symmetry, ER is null at Mn2+ site this is shown to be not true in the neighborhood of ligands for the LiBaF3 host lattice. The quite different shape of ER in normal and inverted perovskite lattices is shown to be already understood considering only the first two shells surrounding the MnF64- complex. The present results demonstrate that the traditional ligand field theory fails to understand the changes undergone by optical and magnetic parameters of a complex when a host lattice is replaced by another one which is not isomorphous. The relevance of present conclusions for understanding the color of Cr3+ -based gemstones is also underlined.

Effect of transition metal composition on electrochemical performance of nickel-manganese-based lithium-rich layer-structured cathode materials in lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konishi, Hiroaki, E-mail: hiroaki.konishi.yj@hitachi.com; Gunji, Akira; Feng, Xiaoliang

2017-05-15

To evaluate the effect of transition metal composition on the electrochemical properties of Li-rich layer-structured cathode materials, Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4) were synthesized, and their electrochemical properties were investigated. As nickel content x increased in Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4), charge-discharge capacities at a low C-rate (0.05 C) decreased. The results obtained by dQ/dV curves indicate that, as the nickel content increased, the discharge capacity below 3.6 V greatly decreased, but that above 3.6 V increased. As the C-rate of the discharge process increased, the discharge reaction of Li{submore » 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2) below 3.6 V greatly decreased. In contrast, that above 3.6 V slightly decreased. This indicates that the discharge reaction above 3.6 V exhibits higher rate performance than that below 3.6 V. For the high-nickel-content cathodes, the ratio of the discharge capacity above 3.6 V to the total discharge capacity was high. Therefore, they exhibited high rate performance. - Graphical abstract: Figure shows the discharge curves of Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2 and 0.3) within potential range of 2.5−4.6 V (vs. Li/Li{sup +}) at 0.05 and 3 C. At low C-rate (0.05 C), the discharge capacity of high-nickel-content cathode (Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2}) was less than that of low-nickel-content cathode (Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2}); however, the discharge potential and capacity of Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2} was higher than those of Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2} at high C-rate (3 C). This means that the increase in Ni/Mn ratio was effective in improving rate-performance.« less

Phase composition, texture, and anisotropy of the properties of Al-Cu-Li-Mg alloy sheets

NASA Astrophysics Data System (ADS)

Betsofen, S. Ya.; Antipov, V. V.; Serebrennikova, N. Yu.; Dolgova, M. I.; Kabanova, Yu. A.

2017-10-01

The formation of the anisotropy of the mechanical properties, the texture, and the phase composition of thin-sheet Al-4.3Cu-1.4Li-0.4Mg and Al-1.8Li-1.8Cu-0.9 Mg alloys have been studied by X-ray diffraction and tensile tests. Various types of anisotropy of the strength properties of the alloys have been revealed: normal anisotropy (strength in the longitudinal direction is higher than that in the transverse direction) in the Al-4.3Cu-1.4Li-0.4Mg alloy and inverse anisotropy in the Al-1.8Li-1.8Cu-0.9Mg alloy. It is shown that the anisotropy of the strength properties is dependent not only on the texture of a solid solution, but also on the content and the texture of the δ' (Al3Li) and T1 (Al2CuLi) phases and their coherency and compatibility of deformation with the matrix.

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5Mn 1.5O 4 Electrodes

DOE PAGES

Qiao, Ruimin; Wray, L. Andrew; Kim, Jung -Hyun; ...

2015-11-11

The LiNi 0.5Mn 1.5O 4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li +). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi 0.5Mn 1.5O 4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi 0.5Mnmore » 1.5O 4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni 2+ and Mn 2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi 0.5Mn 1.5O 4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.« less

Nanosized LiM YMn 2- YO 4 (M = Cr, Co and Ni) spinels synthesized by a sucrose-aided combustion method . Structural characterization and electrochemical properties

NASA Astrophysics Data System (ADS)

Amarilla, J. M.; Rojas, R. M.; Pico, F.; Pascual, L.; Petrov, K.; Kovacheva, D.; Lazarraga, M. G.; Lejona, I.; Rojo, J. M.

Spinels of composition LiM YMn 2- YO 4, M = Cr 3+, Co 3+, or Ni 2+, Y = 0.1 and 1 for the Cr and Co dopants, Y = 0.05 and 0.5 for the Ni sample, have been synthesized by a sucrose-aided combustion method. The samples as prepared require of an additional thermal treatment at 700 °C, 1 h to get stoichiometric single-phase spinels. The samples consist of aggregated particles of small size (45-50 nm) as deduced from transmission electron microscopy and X-ray powder diffraction. The electrochemical behaviour of the six spinels as cathodes in lithium cells has been analysed at 5 and 4 V under high current, 1 C rate. At 5 V the discharge capacity of LiNi 0.5Mn 1.5O 4 is higher than the one shown by LiCrMnO 4 and LiCoMnO 4, and it shows an elevated cyclability, i.e. capacity retention of 85.3% after 100 cycles. At 4 V the discharge capacity is similar for LiNi 0.05Mn 1.95O 4, LiCr 0.1Mn 1.9O 4 and LiCo 0.1Mn 1.9O 4, and all the three spinels show similar and very high cyclability, i.e. capacity retention >90% after 100 cycles. The spinels preserve their starting capacity up to currents as high as 2 C rate. The nanometric size of the samples explains the high rate capability of the synthesized spinels.

Layered oxides-LiNi1/3Co1/3Mn1/3O2 as anode electrode for symmetric rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Yuesheng; Feng, Zimin; Yang, Shi-Ze; Gagnon, Catherine; Gariépy, Vincent; Laul, Dharminder; Zhu, Wen; Veillette, René; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-02-01

High-performance and long-cycling rechargeable lithium-ion batteries have been in steadily increasing demand for the past decades. Nevertheless, the two dominant anodes at the moment, graphite and L4T5O12, suffer from a safety issue of lithium plating (operating voltage at ∼ 0.1 V vs. Li+/Li) and low capacity (175 mAh/g), respectively. Here, we report LiNi1/3Co1/3Mn1/3O2 as an alternative anode material which has a working voltage of ∼1.1 V and a capacity as high as 330 mAh/g at the current rate of C/15. Symmetric cells with both electrodes containing LiNi1/3Co1/3Mn1/3O2 can deliver average discharge voltage of 2.2 V. In-situ XRD, HRTEM and first principles calculations indicate that the reaction mechanism of a LiNi1/3Co1/3Mn1/3O2 anode is comprised mainly of conversion. Both the fundamental understanding and practical demonstrations suggest that LiNi1/3Co1/3Mn1/3O2 is a promising negative electrode material for lithium-ion batteries.

Periodic table of 3d-metal dimers and their ions.

PubMed

Gutsev, G L; Mochena, M D; Jena, P; Bauschlicher, C W; Partridge, H

2004-10-08

The ground states of the mixed 3d-metal dimers TiV, TiCr, TiMn, TiFe, TiCo, TiNi, TiCu, TiZn, VCr, VMn, VFe, VCo, VNi, VCu, VZn, CrMn, CrFe, CrCo, CrNi, CrCu, CrZn, MnFe, MnCo, MnNi, MnCu, MnZn, FeCo, FeNi, FeCu, FeZn, CoNi, CoCu, CoZn, NiCu, NiZn, and CuZn along with their singly negatively and positively charged ions are assigned based on the results of computations using density functional theory with generalized gradient approximation for the exchange-correlation functional. Except for TiCo and CrMn, our assignment agrees with experiment. Computed spectroscopic constants (r(e),omega(e),D(o)) are in fair agreement with experiment. The ground-state spin multiplicities of all the ions are found to differ from the spin multiplicities of the corresponding neutral parents by +/-1. Except for TiV, MnFe, and MnCu, the number of unpaired electrons, N, in a neutral ground-state dimer is either N(1)+N(2) or mid R:N(1)-N(2)mid R:, where N(1) and N(2) are the numbers of unpaired 3d electrons in the 3d(n)4s(1) occupation of the constituent atoms. Combining the present and previous results obtained at the same level of theory for homonuclear 3d-metal and ScX (X=Ti-Zn) dimers allows one to construct "periodic" tables of all 3d-metal dimers along with their singly charged ions.

The application of Westcott Formalism k0 NAA method to estimate short and medium lived elements in some Ghanaian herbal medicines complemented by AAS

NASA Astrophysics Data System (ADS)

Ayivor, J. E.; Okine, L. K. N.; Dampare, S. B.; Nyarko, B. J. B.; Debrah, S. K.

2012-04-01

The epithermal neutron shape factor, α of the inner and outer irradiation sites of the Ghana Research Reactor-1 (GHARR-1) was determined obtaining results of 0.105 for the inner (Channel 1) Irradiation site and 0.020 for the outer (channel 6) irradiation site. The neutron temperatures for the inner and outer irradiation sites were 27 °C and 20 °C, respectively. The α values used in Westcott Formalism k0 INAA was applied to determine multi elements in 13 Ghanaian herbal medicines used by the Centre for Scientific Research into Plant Medicine (CSRPM) for the management of various diseases complemented by Atomic Absorption Spectrometry. They are namely Mist. Antiaris, Mist. Enterica, Mist. Morazia, Mist. Nibima, Mist. Modium, Mist. Ninger, Mist Sodenia, Mist. Tonica, Chardicca Powder, Fefe Powder, Olax Powder, Sirrapac powder and Lippia Tea. Concentrations of Al, As, Br, K, Cl, Cu, Mg, Mn, Na and V were determined by short and medium irradiations at a thermal neutron flux of 5×1011 ncm-2 s-1. Fe, Cr, Pb, Co, Ni, Sn, Ca, Ba, Li and Sb were determined using Atomic Absorption Spectrometry (AAS). Ba, Cu, Li and V were present at trace levels whereas Al, Cl, Na, Ca were present at major levels. K, Br, Mg, Mn, Co, Ni, Fe and Sb were also present at minor levels. Arsenic was not detected in all samples. Standard Reference material, IAEA-V-10 Hay Powder was simultaneously analysed with samples. The precision and accuracy of the method using real samples and standard reference materials were evaluated and within ±10% of the reported value. Multivariate analytical techniques, such as cluster analysis (Q-mode and R-mode CA) and principal component analysis (PCA)/factor analysis (FA), have been applied to evaluate the chemical variations in the herbal medicine dataset. All the 13 samples may be grouped into 2 statistically significant clusters (liquid based and powdered herbal medicines), reflecting the different chemical compositions. R-mode CA and PCA suggest common sources for Co, Mg, Fe, Ca, Cr, Ni, Sn, Li and Sb and Na, V, Cl, Mn, Al, Br and K. The PCA/FA identified 3 dominant factors as responsible for the data structure, explaining 84.5% of the total variance in the dataset.

Synthesis and Electrochemical Performance of Urea Assisted Pristine LiMn2O4 Cathode for Li Ion Batteries

NASA Astrophysics Data System (ADS)

Iqbal, Azhar; Iqbal, Yousaf; Khan, Abdul Majeed; Ahmed, Safeer

2017-12-01

We report the synthesis of electrochemically active LiMn2O4 nanoparticles at varied temperature and pH values by sol-gel method using urea as a chelating and combusting agent. The effect of pH and annealing temperature on the structure, morphology and electrochemical performance was evaluated. The results obtained by XRD, SEM, TEM, and FTIR show that LiMn2O4 has uniform porous morphology and highly crystalline particles that can be obtained at pH 7.0 and 8.0 and at a relatively lower temperature of 600°C. Cyclic voltammetry measurements showed reversible redox reactions with fast kinetics corresponding to Li ions intercalation/deintercalation at 600°C at neutral pH 7.0. Charge/discharge studies carried out at a current rate of 40 mA g-1 reveal that LiMn2O4 synthesized at 600°C and pH 7.0 has the best structural stability and excellent cycling performance.

Evolution of Grain Boundary Precipitates in an Al-Cu-Li Alloy During Aging

NASA Astrophysics Data System (ADS)

Ott, Noémie; Kairy, Shravan K.; Yan, Yuanming; Birbilis, Nick

2017-01-01

The grain boundary microstructure of Al-Cu-Li alloy AA2050 was investigated for different isothermal aging times to rationalize intergranular corrosion (IGC) characteristics. In the underaged condition, the dominant grain boundary precipitates are fine T1 (Al2CuLi). Extended aging revealed that grain boundaries were decorated by large T1 precipitates and S' phase (Al2CuMg), with S' growth not dimensionally constrained. Such a transition in the precipitate type at grain boundaries is a unique feature of the Al-Cu-Li system.

Microstructure and microwave magnetic properties of Low-Firing Li0.42Zn0.27Ti0.11Mn0.1Fe2.1O4 ferrite

NASA Astrophysics Data System (ADS)

Xie, Fei; Jia, Lijun; Shen, Qihang; Qiu, Hua; Zhang, Huaiwu

2018-03-01

Low firing temperature and excellent gyromagnetic properties such as high remanence square ratio and narrow ferromagnetic resonance line width are required for the application in nonreciprocal microwave ferrite devices based on low temperature cofired ceramics (LTCC) technology. In this research, Bi2O3-Li2CO3 mixture was introduced as the sintering agent to lower the sintering temperature of Li0.42Zn0.27Ti0.11Mn0.1Fe2.1O4 ferrite. The influence of Bi2O3-Li2CO3 mixture upon the phase composition, composite microstructures and gyromagnetic properties of LiZnTiMn ferrite sintered at low temperature has been investigated for LTCC integration applications. With a proper amount of Bi2O3-Li2CO3 mixture, the sintering temperature of LiZnTiMn ferrite successfully reduced to below 900°C from 1100°C without degradation of magnetic properties, meanwhile, both of saturation flux density and remanence square ratio were increased.

First-principles investigation of the structural characteristics of LiMO2 cathode materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Kim, Yongseon

2015-11-01

The structural features related to the defects of LiMO2 (M = Ni, Co, Mn) cathode materials for lithium secondary batteries were investigated by a simulation of phase diagrams based on first-principle calculations. Crystal models with various types of point defects were designed and dealt with as independent phases, which enabled an examination of the thermodynamic stability of the defects. A perfect phase without defects appeared to be the most stable for LiCoO2, whereas the formation of Li vacancies, O vacancies, and antisites between Li and Ni was thermodynamically unavoidable for LiNiO2. The introduction of both Co and Mn in LiNiO2 was effective in reducing the formation of point defects, but increasing the relative amount of Mn was undesirable because the antisite defect remained stable with Mn doping. The simulation showed good agreement with the experimental data and previous reports. Therefore, the method and the results of this study are expected to be useful for examining the synthesis, structure and related properties of layer-structured cathode materials.

Critical Elements in Fly Ash from the Combustion of Bituminous Coal in Major Polish Power Plants

NASA Astrophysics Data System (ADS)

Bielowicz, Barbara; Botor, Dariusz; Misiak, Jacek; Wagner, Marian

2018-03-01

The concentration of critical elements, including such REE as Fe, Co, W, Zn, Cr, Ni, V, Mn, Ti, Ag, Ga, Ta, Sr, Li, and Cu, in the so-called fly ash obtained from the 9 Polish power plants and 1 thermal power station has been determined. The obtained values, compared with the global average concentration in bituminous coal ash and sedimentary rocks (Clarke values), have shown that the enrichment of fly ash in the specified elements takes place in only a few bituminous coal processing sites in Poland. The enrichment factor (EF) is only slightly higher (the same order of magnitude) than the Clarke values. The enrichment factor in relation to the Clarke value in the Earth's crust reached values above 10 in all of the examined ashes for the following elements: Cr, Ni, V, W, and, in some ash samples, also Cu and Zn. The obtained values are low, only slightly higher than the global average concentrations in sedimentary rocks and bituminous coal ashes. The ferromagnetic grains (microspheres) found in bituminous coal fly ashes seem to be the most economically prospective in recovery of selected critical elements. The microanalysis has shown that iron cenospheres and plerospheres in fly ash contain, in addition to enamel and iron oxides (magnetite and hematite), iron spinels enriched in Co, Cr, Cu, Mn, Ni, W, and Zn.

Doping Li-rich cathode material Li2MnO3 : Interplay between lattice site preference, electronic structure, and delithiation mechanism

NASA Astrophysics Data System (ADS)

Hoang, Khang

2017-12-01

We report a detailed first-principles study of doping in Li2MnO3 , in both the dilute doping limit and heavy doping, using hybrid density-functional calculations. We find that Al, Fe, Mo, and Ru impurities are energetically most favorable when incorporated into Li2MnO3 at the Mn site, whereas Mg is most favorable when doped at the Li sites. Nickel, on the other hand, can be incorporated at the Li site and/or the Mn site, and the distribution of Ni over the lattice sites can be tuned by tuning the material preparation conditions. There is a strong interplay among the lattice site preference and charge and spin states of the dopant, the electronic structure of the doped material, and the delithiation mechanism. The calculated electronic structure and voltage profile indicate that in Ni-, Mo-, or Ru-doped Li2MnO3 , oxidation occurs on the electrochemically active transition-metal ion(s) before it does on oxygen during the delithiation process. The role of the dopants is to provide charge compensation and bulk electronic conduction mechanisms in the initial stages of delithiation, hence enabling the oxidation of the lattice oxygen in the later stages. This work thus illustrates how the oxygen-oxidation mechanism can be used in combination with the conventional mechanism involving transition-metal cations in design of high-capacity battery cathode materials.

In-situ TEM on the coalescence of birnessite manganese dioxides nanosheets during lithiation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Ke; Kuang, Min; Zhang, Yuxin

2016-07-15

Highlights: • Evolution of MnO{sub 2} nanosheets during lithiation was in situ observed. • MnO{sub 2} was reacted with Li to form Mn and LiO{sub 2}. • Nanosheets expanded and aggregated due to lithiation. - Abstract: Nanostructure is believed to produce great benefits for anode materials in lithium ion batteries (LIBs) by enhancing lithium ion transfer, accommodating large volume change and increasing surface area. Whether the nanostructure (especially the porous nanostructure) could be well held during charging/discharging process is one of the most commonly concerned issues in LIBs research. The dynamic evolution of birnessite manganese dioxides nanosheets during lithiation processmore » is investigated by in-situ transmission electron microscopy (TEM) for the first time. The TiO{sub 2}@MnO{sub 2} core-shell nanowires are used as the anode and Li metal as the counter electrode inside the TEM. Interestingly, the lithiation process is confirmed as MnO{sub 2} and Li converting to Li{sub 2}O and Mn. The original porous structure of the nanosheets is hard to preserve during lithiation process due to lithiation-induced contact flattening.« less

A comparative study of Si-containing electrolyte additives for lithium ion battery: Which one is better and why is it better

NASA Astrophysics Data System (ADS)

Wang, Kang; Xing, Lidan; Zhu, Yunmin; Zheng, Xiongwen; Cai, Dandan; Li, Weishan

2017-02-01

Influence of two Si-containing electrolyte additives, tris(trimethylsilyl)borate (TMSB) and tris(trimethylsilyl)phosphate (TMSP), on the cyclic stability of high voltage LiNi0.5Mn1.5O4 electrode has been systematically studied in this work. The capacity retention of LiNi0.5Mn1.5O4 cycling in STD (1M LiPF6/EC: EMC = 3:7), TMSB- and TMSP-containing electrolytes is 23%, 85% and 71% after 600 cycles at 1C rate, respectively, revealing that the ability of TMSB on improving the cyclic performance of LiNi0.5Mn1.5O4 is superior to that of TMSP. Experimental and theoretical characterizations show that the preferential reaction of both TMSB and TMSP generates thin and uniform film on LiNi0.5Mn1.5O4 surface, which effectively suppress the continuous oxidation reaction of electrolyte. While the film generated from TMSB, which contains B and Si-rich compounds, shows better ability on restraining the growth of interfacial resistance during cycling, resulting in better cyclic stability of LiNi0.5Mn1.5O4 than that of TMSP.

3-D dumbbell-like LiNi1/3Mn1/3Co1/3O2 cathode materials assembled with nano-building blocks for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ryu, Won-Hee; Lim, Sung-Jin; Kim, Won-Keun; Kwon, HyukSang

2014-07-01

Dumbbell-like microsphere carbonate precursors including multi-transition metal components (Ni1/3Mn1/3Co1/3CO3) assembled with nano-building blocks were synthesized by urea-assisted solvo/hydrothermal method, and layered cathode materials (LiNi1/3Mn1/3Co1/3O2) were subsequently prepared using the similarly shaped carbonate precursors for Li-ion batteries. For the synthesis of hierarchical microsphere structures, the partial addition of viscous organic solvent (e.g. ethylene glycol) in aqueous solution played a crucial role, not only in suppressing the sudden particle growth but also in regulating the directional crystallization of carbonate particles on the surface. The dumbbell-like LiNi1/3Mn1/3Co1/3O2 assembled with nanocubes prepared via the urea-assisted solvo/hydrothermal method exhibited better electrochemical characteristics, such as initial discharge capacity, cyclic performance, and rate-capability as a cathode material of Li-ion batteries, compared with the LiNi1/3Mn1/3Co1/3O2 materials prepared via the conventional co-precipitation method.

TEM Studies: The Key for Understanding the Origin of the 3.3 V and 4.5 V Steps Observed in LiMn 2O 4-based Spinels

NASA Astrophysics Data System (ADS)

Dupont, L.; Hervieu, M.; Rousse, G.; Masquelier, C.; Palacín, M. R.; Chabre, Y.; Tarascon, J. M.

2000-12-01

Transmission electron microscopy (TEM) measurements were performed on electrochemically partially delithiated prepared spinel Li1-xMn2O4 samples. The potential-composition profile of LiMn2O4 exhibits (besides the two plateaus at 4.05 and 4.1 V) two additional redox steps of identical capacity at 4.5 and 3.3/3.95 V. We found by TEM studies that these extra steps are the signature of a reversible phase transition between LiMn2O4 spinel type structure and a new Li1-xMn2O4 double hexagonal (DH) type structure (a≈5.8 Å, c≈8.9 Å, P63mc). The latter is isotypic with DH LiFeSnO4. Selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) made it possible to identify the mechanism by which this cubic-DH phase transition occurs within a particle. Based on the structural findings the origin as well as the similar electrochemical capacity of the 3.3/3.95 and 4.5 V anomalies are explained.

The effect of cation doping on spinel LiMn 2O 4: a first-principles investigation

NASA Astrophysics Data System (ADS)

Shi, Siqi; Ouyang, Chuying; Wang, Ding-sheng; Chen, Liquan; Huang, Xuejie

2003-05-01

The effect of the cation doping on the electronic structure of spinel LiM yMn 2- yO 4 (M=Cr, Mn, Fe, Co and Ni) has been calculated by first-principles. Our calculation shows that new M-3d bands emerge in the density of states compared with that in LiMn 2O 4. Simultaneously, the new O-2p bands appear accordingly in almost the same energy range around the Fermi energy owing to the M-3d/O-2p interaction. It is found that the appearance of new O-2p bands in the lower energy position results in a higher intercalation voltage. Consequently, the origin of higher intercalation voltage in LiM yMn 2- yO 4 can be ascribed to the lower O-2p level introduced by the doping cation M.

Influence of thermal history on the electrochemical properties of Li[Ni0.5Mn1.5]O4

NASA Astrophysics Data System (ADS)

Liu, Guoqiang; Park, Kyu-Sung; Song, Jie; Goodenough, John B.

2013-12-01

The oxygen-stoichiometric spinel Li[Ni0.5Mn1.5]O4 is an insulator with ordered Ni(II) and Mn(IV). Although it delivers 4.7 V versus Li, the ordered phase gives poor performance as the cathode of a Li-ion battery. Here we demonstrate control of the degree of cation order by adjusting the oxygen stoichiometry with thermal history of the synthesis rather than by doping 2M(III) for Ni(II) + Mn(IV) (M = Cr, Mn, Fe, Co, Al, Ga). We report retention of capacity near 100 mAh g-1 at room temperature at 10C/10C charge/discharge rate with little capacity fade; at 55 °C, a capacity fade occurs as a result of reaction with the electrolyte, but it is reduced to a level comparable to that obtained by doping.

Effect of Copper on Corrosion of Forged AlSi1MgMn Automotive Suspension Components

NASA Astrophysics Data System (ADS)

Koktas, Serhan; Gokcil, Emre; Akdi, Seracettin; Birol, Yucel

2017-09-01

Recently, modifications in the alloy composition and the manufacturing process cycle were proposed to achieve a more uniform structure with no evidence of coarse grains across the section of the AlSi1MgMn alloys. Cu was added to the AlSi1MgMn alloy to improve its age hardening capacity without a separate solution heat treatment. However, Cu addition degrades the corrosion resistance of this alloy due to the formation of Al-Cu precipitates along the grain boundaries that are cathodic with respect to the aluminum matrix and thus encourage intergranular corrosion. The present work was undertaken to identify the impact of Cu addition on the corrosion properties of AlSi1MgMn alloys with different Cu contents. A series of AlSi1MgMn alloys with 0.06-0.89 wt.% Cu were tested in order to identify an optimum level of Cu addition.

Synthesis of Li2MnSiO4-graphene composite and its electrochemical performances as a cathode material for lithium ion batteries.

PubMed

Kim, Jeonghyun; Song, Taeseup; Park, Hyunjung; Yuh, Junhan; Paik, Ungyu

2014-10-01

The Li2MnSiO4 is a promising candidate as a cathode for lithium ion batteries due to its large theoretical capacity of 330 mA h g(-1) and high thermal stability. However, the problems related to low electronic conductivity and large irreversible capacity at the first cycle limits its practical use as a Li-ion cathode material. We have developed a carbon coated Li2MnSiO4-graphene composite electrode to overcome these problems. Our designed electrode exhibits high reversible capacity of 301 mA h g(-1), with a high initial coulombic efficiency, and a discharge capacity at current rate of 0.5 C, that is double value of carbon coated Li2MnSiO4-carbon black composite electrode. These significant improvements are attributed to fast electron transport along the graphene sheet.

Cu-Mn-Fe alloys and Mn-rich amphiboles in ancient copper slags from the Jabal Samran area, Saudi Arabia: With synopsis on chemistry of Fe-Mn(III) oxyhydroxides in alteration zones

NASA Astrophysics Data System (ADS)

Surour, Adel A.

2015-01-01

In the Jabal Samran area (western Saudi Arabia), secondary copper mineralization in a NE-trending shear zone in which the arc metavolcanic host rocks (dacite-rhyodacite) show conjugate fractures and extensive hydrothermal alteration and bleaching. The zones contain frequent Fe-Mn(III) oxyhydroxides (FeOH-MnOH) that resulted from oxidation of pyrite and Mn-bearing silicates. In the bleached part, the groundmass is represented by Fe-bearing interstratified illite-smectite with up to 4.02 wt% FeOt. FeOH-MnOH are pre-weathering phases formed by hydrothermal alteration in a submarine environment prior to uplifting. Five varieties of FeOH are distinguished, four of them are exclusively hydrothermal with ∼20 wt% H2O whereas the fifth contains ∼31-33 wt% H2O and might represent reworking of earlier hydrothermal FeOH phases by weathering. FeOH fills thin fractures in the form of veinlets and crenulated laminae or as a pseudomorph for pyrite, goethite and finally ferrihydrite, and this oxyhydroxide is characterized by positive correlation of Fe2O3 with SiO2 and Al2O3. On the other hand, MOH shows positive correlation between MnO2 and Al2O3 whereas it is negative between Fe2O3 and SiO2. Paratacamite is the most common secondary copper mineral that fills fractures and post-dates FeOH and MnOH. It is believed that Cl- in the structure of paratacamite represents inherited marine storage rather than from surfacial evaporates or meteoric water. The mineralogy of slags suggests a complicated mineral assemblage that includes native Cu prills, synthetic spinifixed Mn-rich amphiboles with 16.73 wt% MnO, brown glass and Ca-Mn-Fe phase close to the olivine structure. EMPA indicate that the some Cu prills have either grey discontinuous boarder zone of S-rich Mn-Cu alloy (with up to 21.95 wt% S and 19.45 wt% Mn) or grey Cu-Mn-Fe alloy (with up to 15.9 wt% Cu, 39. 12 wt% Mn and 61.64 wt% Fe). Mn in the Cu prills is expelled inward as Cu-Mn-Fe alloy inclusions whereas S is expelled outward as S-rich Mn-Cu alloy crust. Remains in the Samran smelter sites suggest the use of charcoal as a source of energy, quartzite as a flux and an air-cooling technique was used.

Cu+ emission in Li2BPO5 material for thermoluminescence dosimetry

NASA Astrophysics Data System (ADS)

Puppalwar, S. P.; Dhoble, S. J.; Kumar, Animesh

2012-05-01

In this study, Li2BPO5 doped with Cu and that co-doped with Mg are synthesized by the wet chemical technique and exposed to γ rays of 60Co to determine their thermoluminescence (TL) properties. The X-ray diffraction technique shows the crystalline nature of the prepared material. The photoluminescence (PL) emission spectra of Li2BPO5:Cu phosphor show the strong prominent peak at 368 nm in the violet region of the visible spectrum due to the transition of 3d94s1 ↔ 3d10 of monovalent copper ion. The PL emission of Li2BPO5:Cu is enhanced by the addition of Mg. The TL glow curves of γ-irradiated Li2BPO5:Cu sample show one glow peak at 143°C, indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak of Li2BPO5:Cu are calculated using the glow curve shape (Chen's) method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. A linear TL response is observed in Li2BPO5:Cu in a long span of exposures. The sensitivity of Li2BPO5:Cu sample is observed to be 7.8 times that of (TLD-100) LiF:Mg, Ti.

Magnetic order induces symmetry breaking in the single-crystalline orthorhombic CuMnAs semimetal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Emmanouilidou, Eve; Cao, Huibo; Tang, Peizhe

2017-12-04

Recently, orthorhombic CuMnAs has been proposed to be a magnetic material where topological fermions exist around the Fermi level. Here we report the magnetic structure of the orthorhombic Cu 0.95MnAs and Cu 0.98Mn 0.96As single crystals. While Cu 0.95MnAs is a commensurate antiferromagnet below 360 K with a propagation vector of k = 0,Cu 0.98Mn 0.96As undergoes a second-order paramagnetic to incommensurate antiferromagnetic phase transition at 320 K with k = (0.1,0,0), followed by a second-order incommensurate to commensurate antiferromagnetic phase transition at 230 K. In the commensurate antiferromagnetic state, the Mn spins order parallel to the crystallographic b axismore » but antiparallel to their nearest neighbors, with the spin orientation along the b axis. This magnetic order breaks S 2z, the two-fold rotational symmetry around the c axis, resulting in finite band gaps at the crossing point and the disappearance of the massless topological fermions. Furthermore, our first-principles calculations suggest that orthorhombic CuMnAs can still host spin-polarized surface states and signature induced by nontrivial topology, which makes it a promising candidate for antiferromagnetic spintronics.« less

Li1.2Mn0.6Ni0.1Co0.1O2 microspheres constructed by hierarchically arranged nanoparticles as lithium battery cathode with enhanced electrochemical performance

NASA Astrophysics Data System (ADS)

Remith, P.; Kalaiselvi, N.

2014-11-01

Novel lithium-rich layered Li1.2Mn0.6Ni0.1Co0.1O2 microspheres containing hierarchically arranged and interconnected nanostructures have been synthesized by a combination of template-free co-precipitation and solid-state methods. The in situ formed γ-MnO2 spherical template upon co-precipitation gets sacrificed during the course of solid-state fusion of cobalt, nickel and lithium precursors to produce the title compound in the form of microspheres constructed by nanoparticles as building blocks. Porous and hollow microspheres of Li1.2Mn0.6Ni0.1Co0.1O2 are formed out of the spontaneous aggregation of nanoparticles, obtained from the custom-designed synthesis protocol. The growth mechanism of Li1.2Mn0.6Ni0.1Co0.1O2 spheres could be understood in terms of the Kirkendall effect and Ostwald ripening. The nanocrystalline Li1.2Mn0.6Ni0.1Co0.1O2 compound is obtained as a solid solution consisting of rhombohedral R3&cmb.macr;m and monoclinic C2/m group symmetries, as evidenced by XRD, Raman spectra and HRTEM equipped with FFT and STEM. The currently synthesized Li1.2Mn0.6Ni0.1Co0.1O2 cathode exhibits an appreciable discharge capacity of 242 mA h g-1 at a current density of 50 mA g-1, due to the synergistic effect of the capacity obtained from the rhombohedral and monoclinic phases.Novel lithium-rich layered Li1.2Mn0.6Ni0.1Co0.1O2 microspheres containing hierarchically arranged and interconnected nanostructures have been synthesized by a combination of template-free co-precipitation and solid-state methods. The in situ formed γ-MnO2 spherical template upon co-precipitation gets sacrificed during the course of solid-state fusion of cobalt, nickel and lithium precursors to produce the title compound in the form of microspheres constructed by nanoparticles as building blocks. Porous and hollow microspheres of Li1.2Mn0.6Ni0.1Co0.1O2 are formed out of the spontaneous aggregation of nanoparticles, obtained from the custom-designed synthesis protocol. The growth mechanism of Li1.2Mn0.6Ni0.1Co0.1O2 spheres could be understood in terms of the Kirkendall effect and Ostwald ripening. The nanocrystalline Li1.2Mn0.6Ni0.1Co0.1O2 compound is obtained as a solid solution consisting of rhombohedral R3&cmb.macr;m and monoclinic C2/m group symmetries, as evidenced by XRD, Raman spectra and HRTEM equipped with FFT and STEM. The currently synthesized Li1.2Mn0.6Ni0.1Co0.1O2 cathode exhibits an appreciable discharge capacity of 242 mA h g-1 at a current density of 50 mA g-1, due to the synergistic effect of the capacity obtained from the rhombohedral and monoclinic phases. Electronic supplementary information (ESI) available: Fig. S1 represents the STEM elemental mapping of pristine Li1.2Mn0.6Ni0.1Co0.1O2. Fig. S2 is the EDX spectrum obtained from HRTEM and Fig. S3 is the SAED pattern. Fig. S4 shows the room temperature conductivity plot and Fig. S5 shows the comparison of the discharge capacity values of LiMn1/3Ni1/3Co1/3O2 and Li1.2Mn0.6Ni0.1Co0.1O2 cathodes and Table 1 shows the d spacing values corresponding to different space group symmetries, derived from XRD and TEM studies. See DOI: 10.1039/c4nr04314f

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2007-08-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Handbook of Isotopes in the Cosmos

NASA Astrophysics Data System (ADS)

Clayton, Donald

2003-09-01

List of illustrations; Preface; Introduction; 1. Hydrogen (H); 2. Helium (He); 3. Lithium (Li); 4. Beryllium (Be); 5. Boron (B); 6. Carbon (C); 7. Nitrogen (N); 8. Oxygen (O); 9. Fluorine (F); 10. Neon (Ne); 11. Sodium (Na); 12. Magnesium (Mg); 13. Aluminium (Al); 14. Silicon (Si); 15. Phosphorous (P); 16. Sulphur (S); 17. Chlorine (Cl); 18. Argon (Ar); 19. Potassium (K); 20. Calcium (Ca); 21. Scandium (Sc); 22. Titanium (Ti); 23. Vanadium (V); 24. Chromium (Cr); 25. Manganese (Mn); 26. Iron (Fe); 27. Cobalt (Co); 28. Nickel (Ni); 29. Copper (Cu); 30. Zinc (Zn); 31. Gallium (Ga); Glossary.

Tuning of Thermal Stability in Layered Li(NixMnyCoz)O2.

PubMed

Zheng, Jiaxin; Liu, Tongchao; Hu, Zongxiang; Wei, Yi; Song, Xiaohe; Ren, Yang; Wang, Weidong; Rao, Mumin; Lin, Yuan; Chen, Zonghai; Lu, Jun; Wang, Chongmin; Amine, Khalil; Pan, Feng

2016-10-12

Understanding and further designing new layered Li(Ni x Mn y Co z )O 2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co) 3 -O-Li 3-x' ): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states from the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, and oxygen coordinated with more nickel (especially with high valence state) in LSCU becomes more unstable at a fixed delithiation state. The Ni/Li mixing would decrease the thermal stability of the "Ni═Mn" group NMC materials but benefit the thermal stability of "Ni-rich" group, because the Ni in the Li layer would form 180° Ni-O-Ni super exchange chains in "Ni-rich" NMC materials. Mn and Co doping can tune the initial valence state of Ni, local coordination environment of oxygen, and the Ni/Li disorder, thus to tune the thermal stability directly.

Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jiaxin; Liu, Tongchao; Hu, Zongxiang

2016-09-19

Understanding and further designing new layered Li(Ni xMn yCo z)O 2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co) 3-O-Li 3-x'): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states frommore » the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, and oxygen coordinated with more nickel (especially with high valence state) in LSCU becomes more unstable at a fixed delithiation state. The Ni/Li mixing would decrease the thermal stability of the “NiMn” group NMC materials but benefit the thermal stability of “Ni-rich” group, because the Ni in the Li layer would form 180° Ni-O-Ni super exchange chains in “Ni-rich” NMC materials. Mn and Co doping can tune the initial valence state of Ni, local coordination environment of oxygen, and the Ni/Li disorder, thus to tune the thermal stability directly.« less

Patterning of silver nanoparticles on visible light-sensitive Mn-doped lithium niobate photogalvanic crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Xiaoyan; Ohuchi, Fumio; Hatano, Hideki

2011-08-01

Visible light-induced polarization-dependent photochemical deposition of silver nanoparticles (AgNPs) has been demonstrated using Mn-doped congruent LiNbO{sub 3} (CLN) single crystals. Mn-doped CLN has a strong absorption over a wide region of the visible spectrum that allowed effective visible light irradiation for photochemical deposition. The AgNPs deposition on Mn-doped CLN was compared with that on non-doped congruent LiNbO{sub 3}, and together these further confirmed that the photochemical deposition on LiNbO{sub 3} is caused by the strong photogalvanic effect.

The effects of copper, manganese and zinc on plant growth and elemental accumulation in the manganese-hyperaccumulator Phytolacca americana.

PubMed

Zhao, Huijun; Wu, Liangqi; Chai, Tuanyao; Zhang, Yuxiu; Tan, Jinjuan; Ma, Shengwen

2012-09-01

Synchrotron radiation X-ray fluorescence (SRXRF) and inductively coupled plasma mass spectrometry were used to estimate major, minor and trace elements in Cu-, Zn- and Mn-treated Phytolacca americana. The effects of the addition of Cu, Zn and Mn on morphological parameters, such as root length, shoot height, and fresh and dry weights of shoots and roots, were also examined. In addition, the activities of superoxide dismutase (SOD), ascorbate peroxidase (APX), guaiacol peroxidases (GPX) and catalase (CAT) and the expression of Fe-SOD, Cu/Zn-SOD, metallothionein-2 and glutathione S-transferase (GST) exposed to the highest amounts of Cu, Zn or Mn were detected. Our results confirmed the following: (1) Zn supplementation leads to chlorosis, disturbed elemental homeostasis and decreased concentrations of micro- and macroelements such as Fe, Mg, Mn, Ca and K. Cu competed with Fe, Mn and Zn uptake in plants supplemented with 25 μM Cu. However, no antagonistic interactions took place between Cu, Zn, Mn and Fe uptake in plants supplemented with 100 μM Cu. Mn supplementation at various concentrations had no negative effects on elemental deficits. Mn was co-located with high concentrations of Fe and Zn in mature leaves and the concentrations of macro elements were unchanged. (2) P. americana supplemented with increased concentrations of Zn and Cu exhibited lower biomass production and reduced plant growth. (3) When plants were supplemented with the highest Zn and Cu concentrations, symptoms of toxicity corresponded to decreased SOD or CAT activities and increased APX and GPX activities. However, Mn tolerance corresponded to increased SOD and CAT activities and decreased POD and APX activities. Our study revealed that heavy metals partially exert toxicity by disturbing the nutrient balance and modifying enzyme activities that induce damage in plants. However, P. americana has evolved hyper accumulating mechanisms to maintain elemental balance and redox homeostasis under excess Mn. Copyright © 2012 Elsevier GmbH. All rights reserved.

Iron, Manganese and Copper Release from Synthetic Hydroxyapatite

NASA Technical Reports Server (NTRS)

Sutter, B.; Hossner, L. R.; Ming, Douglas W.

1999-01-01

Kinetic stir-flow dissolution experiments were performed on iron- (Fe-SHA), manganese- (Mn-SHA), and copper- (Cu-SHA) containing synthetic hydroxyapatites. Solution treatments consisted of de-ionized water, citric acid and DTPA. Initially, Mn concentrations were higher than Cu concentrations and Fe concentrations were the lowest in all treatments. At later times Mn and Cu concentrations dropped in the DTPA treatment while Fe rose to the concentration similar to Mn and Cu. At all times, metal release concentrations in the water and citric acid treatments followed the trend of Mn>Cu>Fe. Rietveld analysis of x-ray diffraction data and ^31P NMR indicated that the metals substituted for Ca in the SHA structure. However, EPR data suggested that a metal (hydr)oxide phase existed either on the SHA surface or between the SHA crystallites. The metal concentration trend of Mn>Cu>Fe suggested that the initial solution metal concentrations are dependent on the dissolution of (hydr)oxides from SHA surfaces or between SHA crystallites. Similar metal concentrations at later times in the DTPA experiments suggests that metal concentrations were controlled by the release of Mn, Cu, or Fe from the SHA structure.

Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

PubMed

Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu

2015-04-01

There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.

Performance of MnO2 Crystallographic Phases in Rechargeable Lithium-Air Oxygen Cathode

NASA Astrophysics Data System (ADS)

Oloniyo, Olubukun; Kumar, Senthil; Scott, Keith

2012-05-01

Manganese dioxide (MnO2) has been shown to be effective for improving the efficiency of cathodes in lithium-air cells. Different crystallographic phases including α-, β-, and γ-MnO2 nanowires, α-MnO2 nanospheres, and α-MnO2 nanowires on carbon ( α-MnO2/C) were synthesized using the hydrothermal method. Their physical properties were examined using x-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area measurements, and scanning electron microscopy (SEM) and found to be in agreement with the literature. Electrochemical properties of the synthesized catalyst particles were investigated by fabricating cathodes and testing them in a lithium-air cell with lithium hexafluorophosphate in propylene carbonate (LiPF6/PC) and tetra(ethylene glycol)dimethyl ether (LiTFSi/TEGDME) electrolytes. α-MnO2 had the highest discharge capacity in the LiTFSi/TEGDME electrolyte (2500 mAh/g), whilst α-MnO2/C in LiPF6/PC showed a significantly higher discharge capacity of 11,000 mAh/g based on total mass of the catalytic cathode. However, the latter showed poor capacity retention compared with γ-MnO2 nanowires, which was stable for up to 30 cycles. The reported discharge capacity is higher than recorded in previous studies on lithium-air cells.

Soft chemical synthesis and electrochemical properties of calcium ferrite-type LixMn2O4

NASA Astrophysics Data System (ADS)

Mamiya, Mikito; Tokiwa, Kazuyasu; Akimoto, Junji

2016-04-01

Calcium ferrite (CaFe2O4)-type LixMn2O4 was prepared via high-pressure and soft chemical synthesis method. The framework structure of CaFe2O4-type NaMn2O4 was synthesized from the stoichiometric mixture of Na2CO3 and MnO2 annealed by 1273 K for 1 h under 4.5 GPa. Na/Li ion-exchange of the CaFe2O4-type NaMn2O4 was carried out by soaking molten LiNO3 at 633 K for 12 h. The electrochemical properties of the ion-exchanged CaFe2O4-type LixMn2O4 were measured. The initial discharge profile in the voltage range from 4.0 to 1.0 V showed 458 mAh g-1 of the discharge capacity with two plateaus near 3.7 V and 2.7 V (vs. Li/Li+). The discharge capacity was decreased with increasing the cycle number. After 30 cycles, the capacity was decreased to 375 mAh g-1. When the range was set between 4.8 and 3.0 V, the discharge capacity was 113 mAh g-1 in initial, and 111 mAh g-1 after 50th cycle. The reference CaFe2O4-type LiMn2O4 was prepared via one-step high-pressure synthesis and compared the electrochemical properties with the ion-exchanged sample. The initial discharge capacity of the one-step synthesized one was 108 mAh g-1 at 1.0 V (vs. Li/Li+), which was 73% lower than the value of the ion-exchanged one.

Electrochemical Properties of the LiNi0.6Co0.2Mn0.2O2 Cathode Material Modified by Lithium Tungstate under High Voltage.

PubMed

Fu, Jiale; Mu, Daobin; Wu, Borong; Bi, Jiaying; Cui, Hui; Yang, Hao; Wu, Hanfeng; Wu, Feng

2018-05-31

An amount (5 wt %) of lithium tungstate (Li 2 WO 4 ) as an additive significantly improves the cycle and rate performances of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode at the cutoff voltage of 4.6 V. The 5 wt % Li 2 WO 4 -mixed LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode delivers a reversible capacity of 199.2 mA h g -1 and keeps 73.1% capacity for 200 cycles at 1 C. It retains 67.4% capacity after 200 cycles at 2 C and delivers a discharge capacity of 167.3 mA h g -1 at 10 C, while those of the pristine electrode are only 44.7% and 87.5 mA h g -1 , respectively. It is shown that the structure of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode material is not affected by mixing Li 2 WO 4 . The introduced Li 2 WO 4 effectively restrains the LiPF 6 and carbonate solvent decomposition by consuming PF 5 at high cutoff voltage, forming a stable cathode/electrolyte interface film with low resistance.

Li-adsorption on doped Mo2C monolayer: A novel electrode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Mehta, Veenu; Tankeshwar, K.; Saini, Hardev S.

2018-04-01

A first principle calculation has been used to study the electronic and magnetic properties of pristine and N/Mn-doped Mo2C with and without Li-adsorption. The pseudopotential method implemented in SIESTA code based on density functional theory with generalized gradient approximation (GGA) as exchange-correlation (XC) potential has been employed. Our calculated results revealed that the Li gets favorably adsorbed on the hexagonal centre in pristine Mo2C and at the top of C-atom in case of N/Mn-doped Mo2C. The doping of Mn and N atom increases the adsorption of Li in Mo2C monolayer which may results in enhancement of storage capacity in Li-ion batteries. The metallic nature of Li-adsorbed pristine and N/Mn-doped Mo2C monolayer implies a good electronic conduction which is crucial for anode materials for its applications in rechargeable batteries. Also, the open circuit voltage for single Li-adsorption in doped Mo2C monolayer comes in the range of 0.4-1.0 eV which is the optimal range for any material to be used as an anode material. Our result emphasized the enhanced performance of doped Mo2C as an anode material in Li-ion batteries.

Copper/carbon coated lithium sodium titanate as advanced anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Kaiqiang; Lin, Xiaoting; Shao, Lianyi; Shui, Miao; Long, Nengbing; Ren, Yuanlong; Shu, Jie

2014-08-01

Core-shell Li2Na2Ti6O14@Cu/C is prepared by a preliminary formation of Li2Na2Ti6O14 by solid state reaction and a following coating process with Cu/C layer by thermal decomposition. The amorphous Cu/C coating layer reveals a thickness of 5 nm on the surface of Li2Na2Ti6O14, which improves the electronic conductivity and charge transfer rate of active materials. As a result, Li2Na2Ti6O14@Cu/C shows lower electrochemical polarization and quicker kinetic behavior compared to bare Li2Na2Ti6O14. Cycled at 50 mA g-1, Li2Na2Ti6O14@Cu/C can deliver a reversible capacity of 120.3 mAh g-1 after 50 cycles, which is much higher than the value of 96.8 mAh g-1 obtained by Li2Na2Ti6O14. Even kept at 400 mA g-1, a reversible lithium storage capacity of 76.3 mAh g-1 can be delivered by Li2Na2Ti6O14@Cu/C. The improved electrochemical properties of Li2Na2Ti6O14 are attributed to the electronic conductive Cu/C coating layer on the surface.

3D Reticular Li1.2Ni0.2Mn0.6O2 Cathode Material for Lithium-Ion Batteries.

PubMed

Li, Li; Wang, Lecai; Zhang, Xiaoxiao; Xue, Qing; Wei, Lei; Wu, Feng; Chen, Renjie

2017-01-18

In this study, a hard-templating route was developed to synthesize a 3D reticular Li 1.2 Ni 0.2 Mn 0.6 O 2 cathode material using ordered mesoporous silica as the hard template. The synthesized 3D reticular Li 1.2 Ni 0.2 Mn 0.6 O 2 microparticles consisted of two interlaced 3D nanonetworks and a mesopore channel system. When used as the cathode material in a lithium-ion battery, the as-synthesized 3D reticular Li 1.2 Ni 0.2 Mn 0.6 O 2 exhibited remarkably enhanced electrochemical performance, namely, superior rate capability and better cycling stability than those of its bulk counterpart. Specifically, a high discharge capacity of 195.6 mA h g -1 at 1 C with 95.6% capacity retention after 50 cycles was achieved with the 3D reticular Li 1.2 Ni 0.2 Mn 0.6 O 2 . A high discharge capacity of 135.7 mA h g -1 even at a high current of 1000 mA g -1 was also obtained. This excellent electrochemical performance of the 3D reticular Li 1.2 Ni 0.2 Mn 0.6 O 2 is attributed to its designed structure, which provided nanoscale lithium pathways, large specific surface area, good thermal and mechanical stability, and easy access to the material center.

Kinetic parameters and structural variations in Cu-Al-Mn and Cu-Al-Mn-Mg shape memory alloys

NASA Astrophysics Data System (ADS)

Canbay, Canan Aksu

2017-02-01

In this work polycrystalline Cu-Al-Mn and Cu-Al-Mn-Mg SMAs were fabricated by arc melting. The thermal analysis was made to determine the characteristic transformation temperatures of the samples and kinetic parameters. Also the effect of Mg on transformation temperatures and kinetic parameters detected. The structural analysis was made to designate the diffraction planes of martensite phase at room temperature and this was supported by optical measurement observations.

One-Step Catalytic Synthesis of CuO/Cu2O in a Graphitized Porous C Matrix Derived from the Cu-Based Metal-Organic Framework for Li- and Na-Ion Batteries.

PubMed

Kim, A-Young; Kim, Min Kyu; Cho, Keumnam; Woo, Jae-Young; Lee, Yongho; Han, Sung-Hwan; Byun, Dongjin; Choi, Wonchang; Lee, Joong Kee

2016-08-03

The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in a highly graphitized porous C matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increasing the rate capability and reversible capacity of metal oxide negative materials for Li- and Na-ion batteries. CuO/Cu2O-GPC is synthesized through a Cu-based metal-organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied and exhibit excellent capacities of 887.3 mAh g(-1) at 60 mA g(-1) after 200 cycles in a Li-ion battery and 302.9 mAh g(-1) at 50 mA g(-1) after 200 cycles in a Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micronanoparticles and highly graphitized porous C formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and resulting high electrochemical performance, CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.

Preparation and magnetic properties of multiferroic CuMnO2 nanoparticles.

PubMed

Kurokawa, Akinobu; Yanoh, Tkuya; Yano, Shinya; Ichiyanagi, Yuko

2014-03-01

CuMnO2 nanoparticles with diameters of 64 nm were synthesized by a novel wet chemical method. An optimized two-step annealing method was developed through the analysis of thermogravimetric differential thermal analysis (TG-DTA) measurements in order to obtain single-phase CuMnO2. A sharp exothermic peak was observed in the DTA curve at approximately 500 K where structural changes of the copper oxides and manganese oxides in the precursor are expected to occur. It is believed that Cu+ ions were oxidized to Cu2+ ions and that Mn2+ ions were oxidized to Mn3+ ions in the Cu-Mn-O system. Deoxidization reactions were also found at approximately 1200 K. The optimized annealing temperature for the first step was determined to be 623 K in air. The optimized annealing temperature for the second step was 1173 K in an Ar atmosphere. Magnetization measurements suggested an antiferromagnetic spin ordering at approximately 50 K. It was expected that Mn3+ spin interactions induced magnetic phase transition affected by definite temperature.

Synthesis and electrochemical characteristics of LiCr xNi 0.5- xMn 1.5O 4 spinel as 5 V cathode materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Hong, Ki-Joo; Sun, Yang-Kook

A series of electrochemical spinel compounds, LiCr xNi 0.5- xMn 1.5O 4 ( x=0, 0.1, 0.3), are synthesized by a sol-gel method and their electrochemical properties are characterized in the voltage range of 3.5-5.2 V. Electrochemical data for LiCr xNi 0.5- xMn 1.5O 4 electrodes show two reversible plateaus at 4.9 and 4.7 V. The 4.9 V plateau is related to the oxidation of chromium while the 4.7 V plateau is ascribed to the oxidation of nickel. The LiCr 0.1Ni 0.4Mn 1.5O 4 electrode delivers a high initial capacity of 152 mAh g -1 with excellent cycleability. The excellent capacity retention of the LiCr 0.1Ni 0.4Mn 1.5O 4 electrode is largely attributed to structural stabilization which results from co-doping (chromium and nickel) and increased theoretical capacity due to substitution of chromium.

Ecosystems supporting clusters of sporadic TSEs demonstrate excesses of the radical-generating divalent cation manganese and deficiencies of antioxidant co factors Cu, Se, Fe, Zn. Does a foreign cation substitution at prion protein's Cu domain initiate TSE?

PubMed

Purdey, M

2000-02-01

Analyses of food chains supporting isolated clusters of sporadic TSEs (CWD in N Colorado, scrapie in Iceland, CJD in Slovakia) demonstrate a consistent 2 1/2+ fold greater concentration of the pro-oxidant divalent cation, manganese (Mn), in relation to normal levels recorded in adjoining TSE-free localities. Deficiencies of the antioxidant co factors Cu/Se/Zn/Fe and Mg, P and Na were also consistently recorded in TSE foodchains. Similarities between the clinical/pathological profile of TSEs and Mn delayed psycho-neurotoxicity in miners are cited, and a novel theory generated which suggests that sporadic TSE results from early life dependence of TSE susceptible genotypes on ecosystems characterised by this specific pattern of mineral imbalance. Low Cu/Fe induces an excessive absorption of Mn in ruminants and an increased oxidation of Mn2+ into its pro oxidant species, Mn3+, which accumulates in mitochondria of CNS astrocytes in Mn SOD deficient genotypes. Deficiencies of scavenger co factors Cu/Zn/Se/Fe in the CNS permits Mn3+ initiated chain reactions of auto-oxidant mediated neuronal degeneration to proliferate, which, in turn, up-regulates the expression of the Cu-metalloprotein, prion protein (PrP). Once the rate of PrP turnover and its demand for Cu exceeds the already depleted supply of Cu within the CNS, PrP can no longer bind sufficient Cu to maintain its conformation. Mn3+ substitutes at the vacated Cu domain on PrP, thus priming up a latent capacity for lethal auto-oxidative activity to be carried along with PrP like a 'trojan horse'; where Mn 3+ serves as the integral 'infectious' transmissible component of the misfolded PrP-cation complex. The Mn overactivation of concanavalin A binding to glycoprotein and Mn-initiated autoxidation results in a diverse pathological profile involving receptor capping, aggregation/modification of CNS membrane/cytoskeletal proteins. TSE ensues. The BSE/nv CJD strain entails a 'synthetic' induction of the same CNS mineral disturbance, where 'in utero' exposure to Cu-chelating insecticides/Mn supplements accelerates the onset of a more virulent 'strain' of adolescent TSE. Copyright 2000 Harcourt Publishers Ltd.

Structural transformations in high-capacity Li 2Cu 0.5Ni 0.5O 2 cathodes

DOE PAGES

Ruther, Rose E.; Pandian, Amaresh Samuthira; Yan, Pengfei; ...

2017-03-09

Cathode materials that can cycle >1 Li + per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li 2Cu 0.5Ni 0.5O 2 has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu 2+/3+ and Ni 2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li 2Cu 0.5Ni 0.5O 2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen evolves before the Cumore » 2+/3+ or Ni 3+/4+ transitions are accessed. In this contribution, X-ray diffraction, transmission electron microscopy (TEM), and transmission X-ray microscopy combined with X-ray absorption near edge structure (TXM–XANES) are used to follow the chemical and structural changes that occur in Li 2Cu 0.5Ni 0.5O 2 during electrochemical cycling. Li 2Cu 0.5Ni 0.5O 2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li 2NiO 2 endmember undergoes. Li 2Cu 0.5Ni 0.5O 2 loses long-range order during charge, but TEM analysis provides clear evidence of particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM–XANES are used to map the different phases that emerge during cycling ex situ and in situ. Lastly, significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

Variation of Aging Precipitates and Mechanical Strength of Al-Cu-Li Alloys Caused by Small Addition of Rare Earth Elements

NASA Astrophysics Data System (ADS)

Ma, Yun-long; Li, Jin-feng

2017-09-01

The effect of small rare earth (RE) addition of 0.11%Ce, 0.2%Er and 0.082%Sc on aging precipitates and mechanical strength of an Al-(3.3-4.2)Cu-1.2Li-X alloy were investigated. It is found that Cu-rich residual particles containing RE element exist in the solutionized alloy, which leads to a decrease of dissolved Cu concentration in the solutionized matrix. Like RE-free alloy, the main aging precipitate types in RE-containing alloy are T1 (Al2CuLi) and θ' (Al2Cu), but their fraction is decreased. The strength of the corresponding alloys is therefore lowered by the small RE addition. Combined with the analysis of some reported references, it is proposed that the effect of small RE addition on Al-Cu-Li alloy strength is also associated with the Cu and Li concentrations and their ratio.

A Gel-Polymer Sn-C/LiMn0.5Fe0.5PO4 Battery Using a Fluorine-Free Salt.

PubMed

Di Lecce, Daniele; Fasciani, Chiara; Scrosati, Bruno; Hassoun, Jusef

2015-09-30

Safety and environmental issues, because of the contemporary use of common liquid electrolytes, fluorinated salts, and LiCoO2-based cathodes in commercial Li-ion batteries, might be efficiently mitigated by employing alternative gel-polymer battery configurations and new electrode materials. Herein we study a lithium-ion polymer cell formed by combining a LiMn0.5Fe0.5PO4 olivine cathode, prepared by simple solvothermal pathway, a nanostructured Sn-C anode, and a LiBOB-containing PVdF-based gel electrolyte. The polymer electrolyte, here analyzed in terms of electrochemical stability by impedance spectroscopy (EIS) and voltammetry, reveals full compatibility for cell application. The LiBOB electrolyte salt and the electrochemically delithiaded Mn0.5Fe0.5PO4 have a higher thermal stability compared to conventional LiPF6 and Li0.5CoO2, as confirmed by thermogravimetric analysis (TGA) and by galvanostatic cycling at high temperature. LiMn0.5Fe0.5PO4 and Sn-C, showing in lithium half-cell a capacity of about 120 and 350 mAh g(-1), respectively, within the gelled electrolyte configuration are combined in a full Li-ion polymer battery delivering a stable capacity of about 110 mAh g(-1), with working voltage ranging from 2.8 to 3.6 V.

Advanced nanostructured materials for energy storage and conversion

NASA Astrophysics Data System (ADS)

Hutchings, Gregory S.

Due to a global effort to reduce greenhouse gas emissions and to utilize renewable sources of energy, much effort has been directed towards creating new alternatives to fossil fuels. Identifying novel materials for energy storage and conversion can enable radical changes to the current fuel production infrastructure and energy utilization. The use of engineered nanostructured materials in these systems unlocks unique catalytic activity in practical configurations. In this work, research efforts have been focused on the development of nanostructured materials to address the need for both better energy conversion and storage, with applications toward Li-O2 battery electrocatalysts, electrocatalytic generation of H2, conversion of furfural to useful chemicals and fuels, and Li battery anode materials. Highly-active alpha-MnO2 materials were synthesized for use as bifunctional oxygen reduction (ORR) and evolution (OER) catalysts in Li-O2 batteries, and were evaluated under operating conditions with a novel in situ X-ray absorption spectroscopy configuration. Through detailed analysis of local coordination and oxidation states of Mn atoms at key points in the electrochemical cycle, a self-switching behavior affecting the bifunctional activity was identified and found to be critical. In an additional study of materials for lithium batteries, nanostructured TiO2 anode materials doped with first-row transition metals were synthesized and evaluated for improving battery discharge capacity and rate performance, with Ni and Co doping at low levels found to cause the greatest enhancement. In addition to battery technology research, I have also sought to find inexpensive and earth-abundant electrocatalysts to replace state-of-the-art Pt/C in the hydrogen evolution reaction (HER), a systematic computational study of Cu-based bimetallic electrocatalysts was performed. During the screening of dilute surface alloys of Cu mixed with other first-row transition metals, materials with ideal hydrogen binding energies were identified. Bulk alloy electrocatalysts with comparable compositions to the model surfaces were synthesized and tested for performance in alkaline, neutral, and acidic conditions. Cu-Ti was found to exhibit the lowest overpotentials and highest overall performance, and was redesigned as a nanoporous catalyst which achieved higher current at lower overpotentials than even commercial Pt/C, with remarkably high stability. Through applying design principles developed during the HER work, self-supported nanoporous Cu-Co alloy catalysts were synthesized for the improvement of product selectivity and overall conversion of reactants in furfural hydro(deoxy)genation. Under vapor-phase reaction conditions, it was found that adding 1% to 10% oxophilic Co in a solid solution with Cu enhanced overall conversion towards products. In particular, a Cu95Co5 alloy produced 64.9% yield of 2-methylfuran at a high sustained total conversion of 85.0% and under moderate temperature conditions, which is the highest 2-methylfuran production reported for non-precious catalysts. Further analysis at a wider range of temperature conditions and sustained reaction time on stream provided a more detailed understanding of the behavior of these nanoporous materials, and possible mechanistic explanations of the high activity for Cu-Co are proposed to aid in the design of new materials with even higher product selectivities.

Aging behavior of an in-situ TiB{sub 2}/Al-Cu-Li-x matrix composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yanwei; Hong, Tianran; Geng, Jiwei

Transmission electron microscopy, differential scanning calorimetry and hardness tests have been performed on an in-situ TiB{sub 2}/Al-3.3Cu-1.0Li-0.60Mg-0.40Ag-0.14Zr-0.13Si composite to study its aging behavior at 175 °C. A cubic phase suspected to be the σ (Al{sub 5}Cu{sub 6}Mg{sub 2}) phase or its variant is precipitated at all aging stages studied, and this phase is not typically observed in the Al-Cu-Li alloys. The primary hardening (aging for 3 h) phases consist of δ′ (Al{sub 3}Li), β′ (Al{sub 3}Zr) and the cubic phase. After aging for 18 h, all precipitates including T{sub 1} (Al{sub 2}CuLi), S (Al{sub 2}CuMg), θ′ (Al{sub 2}Cu), δ′, β′more » and the cubic phase have appeared, and the formation of T{sub 1} and S results in a rapid increase in hardness. With prolonging of aging time, the apparent coarsening of T{sub 1} and S results in a decline in hardness. - Highlights: •The aging behavior of an in-situ TiB{sub 2}/Al-Cu-Li-x composite was studied. •A cubic phase suspected to be σ (Al{sub 5}Cu{sub 6}Mg{sub 2}) or its variant was precipitated. •The hardness change was dominated by the evolution of T{sub 1} (Al{sub 2}CuLi) and S (Al{sub 2}CuMg).« less

Improvement of selective lignin degradation in fungal pretreatment of sweet sorghum bagasse using synergistic CuSO4-syringic acid supplements.

PubMed

Mishra, Vartika; Jana, Asim K; Jana, Mithu Maiti; Gupta, Antriksh

2017-05-15

Sweet sorghum bagasse (SSB) generated in large quantities could be hydrolyzed to sugar and then fermented to green fuels. The hydrolysis of SSB polysaccharides interlocked in recalcitrant lignin network is the major problem. Pretreatment of SSB in SSF by using Coriolus versicolor with CuSO 4 -syringic acid supplements for effects on production of ligninocellulolytic enzymes, lignin degradation and selectivity values (SV) were studied. C. versicolor was selected based on high ligninolytic and low cellulolytic abilily. Individually, CuSO 4 increased the activities of laccase (4.9 folds) and PPO (1.9 folds); syringic acid increased LiP (13 folds), AAO (2.8 folds) and laccase (5.6 folds) resulting in increased lignin degradation and SVs. Combined syringic acid (4.4 μmol g -1 SSB) and CuSO 4 (4.4 μmol g -1 SSB) increased the activities of laccase, LiP, MnP, PPO and AAO by 11.2, 17.6, 2.8, 2.4 and 2.3 folds respectively due to synergistic effect, resulting in maximum lignin degradation 35.9 ± 1.3% (w w -1 ) (1.86 fold) and highest SV 3.07 (4.7 fold). Enzymatic hydrolysis of pretreated SSB yielded higher (∼2.2 times) fermentable sugar. Pretreated SSB was characterized by XRD, SEM, FTIR and TGA/DTG analysis to confirm results. It is possible to improve fungal pretreatment of agricultural waste by combination of supplements. Copyright © 2017 Elsevier Ltd. All rights reserved.

[delta] precipitation in an Al-Li-Cu-Mg-Zr alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, K.S.; Mukhopadhyay, A.K.; Gokhale, A.A.

1994-05-15

AlLi based [delta] phase has an NaTl structure (i.e., a diamond cubic) with a = 0.637nm and is an equilibrium phase in the binary Al-Li system. In heat treated binary Al-Li alloys of appropriate compositions, [delta] phase can format grain boundaries as well as within the grains. In commercially heat treated Al-Li-Cu alloys of 2090 specification, the grain boundary precipitate [delta] of the binary Al-Li system is replaced by a combination of T[sub 2](Al[sub 6]CuLi[sub 3]), R(Al[sub 5]CuLi[sub 3]) and T[sub 1](Al[sub 2]CuLi) phases. In similarly treated Al-Li-Cu-Mg alloys of 8090 specification, the copper rich T[sub 2] phase, present inmore » the form of Al[sub 6]CuLi[sub 3[minus]x]Mg[sub x], is known to be the major coarse g.b. precipitate. The presence of an Al-Li-Cu-Mg based C phase at the grain boundaries of the commercially heat treated 8090 alloys has also been documented. No detailed study has yet been carried out to verify whether the [delta] phase can be present at the grain boundaries of the commercially heat treated 8090 alloys. Given the correlations between the g.b. phase morphology, g.b. phase chemistry, and the stress corrosion cracking resistance of these alloys, it is important that the g.b. precipitates be examined and identified. In this paper results using TEM are presented to show that the [delta] phase can be present in varying amounts at the grain boundaries in an 8090 alloy when heat treated in the temperature range of 170--350 C. An examination is also made of the [delta] precipitation within the grain to establish that the T[sub 2]/[alpha]-Al interface is the dominant nucleation site for the noncoherent [delta] phase.« less

Evaluation of Fe-containing Li2CuO2 on CO2 capture performed at different physicochemical conditions.

PubMed

Yañez-Aulestia, Ana; Ovalle-Encinia, Oscar; Pfeiffer, Heriberto

2018-06-05

Li 2 CuO 2 and different iron-containing Li 2 CuO 2 samples were synthesized by solid state reaction. On iron-containing samples, atomic sites of copper are substituted by iron ions in the lattice (XRD and Rietveld analyses). Iron addition induces copper release from Li 2 CuO 2 , which produce cationic vacancies and CuO, due to copper (Cu 2+ ) and iron (Fe 3+ ) valence differences. Two different physicochemical conditions were used for analyzing CO 2 capture on these samples; (i) high temperature and (ii) low temperature in presence of water vapor. At high temperatures, iron addition increased CO 2 chemisorption, due to structural and chemical variations on Li 2 CuO 2 . Kinetic analysis performed by first order reaction and Eyring models evidenced that iron addition on Li 2 CuO 2 induced a faster CO 2 chemisorption but a higher thermal dependence. Conversely, CO 2 chemisorption at low temperature in water vapor presence practically did not vary by iron addition, although hydration and hydroxylation processes were enhanced. Moreover, under these physicochemical conditions the whole sorption process became slower on iron-containing samples, due to metal oxides presence.

The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Prakash, G. K. S.; Ratnakumar, B. V.

2011-01-01

With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

Synthesis, Structure, and Electrochemical Performance of High Capacity Li 2Cu 0.5Ni 0.5O 2 Cathodes

DOE PAGES

Ruther, Rose E; Zhou, Hui; Dhital, Chetan; ...

2015-09-08

Orthorhombic Li 2NiO 2, Li 2CuO 2, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li 2Cu 0.5Ni 0.5O 2, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li 2CuO 2 are presented. The cycle life of Li 2Cu 0.5Ni 0.5O 2 is shown to depend critically on the voltage window. The formation of Cu 1+ at low voltage and oxygen evolution at highmore » voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.« less

Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

NASA Astrophysics Data System (ADS)

Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

2018-02-01

The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Li-Fang; Ou, Chin-Ching; Striebel, Kathryn A.

The goal of this research was to measure Mn dissolution from a thin porous spinel LiMn{sub 2}O{sub 4} electrode by rotating ring-disk collection experiments. The amount of Mn dissolution from the spinel LiMn{sub 2}O{sub 4} electrode under various conditions was detected by potential step chronoamperometry. The concentration of dissolved Mn was found to increase with increasing cycle numbers and elevated temperature. The dissolved Mn was not dependent on disk rotation speed, which indicated that the Mn dissolution from the disk was under reaction control. The in situ monitoring of Mn dissolution from the spinel was carried out under various conditions.more » The ring currents exhibited maxima corresponding to the end-of-charge (EOC) and end-of-discharge (EOD), with the largest peak at EOC. The results suggest that the dissolution of Mn from spinel LiMn{sub 2}O{sub 4} occurs during charge/discharge cycling, especially in a charged state (at >4.1 V) and in a discharged state (at <3.1 V). The largest peak at EOC demonstrated that Mn dissolution took place mainly at the top of charge. At elevated temperatures, the ring cathodic currents were larger due to the increase of Mn dissolution rate.« less

Three-dimensional sandwich-structured NiMn2O4@reduced graphene oxide nanocomposites for highly reversible Li-ion battery anodes

NASA Astrophysics Data System (ADS)

Huang, Jiarui; Wang, Wei; Lin, Xirong; Gu, Cuiping; Liu, Jinyun

2018-02-01

A sandwich-structured NiMn2O4@reduced graphene oxide (NiMn2O4@rGO) nanocomposite consisting of ultrathin NiMn2O4 sheets uniformly anchored on both sides of a three-dimensional (3D) porous rGO is presented. The NiMn2O4@rGO nanocomposites prepared through a dipping process combining with a hydrothermal method show a good electrochemical performance including a high reversible capability of 1384 mAh g-1 at 1000 mA g-1 over 1620 cycles, and an superior rate performance. Thus, a full cell consisting of a commercial LiCoO2 cathode and the NiMn2O4@rGO anode delivers a stable capacity of about 1046 mAh g-1 (anode basis) after cycling at 50 mA g-1 for 60 times. It is demonstrated that the 3D porous composite structure accommodates the volume change during the Li+ insertion/extraction process and facilitates the rapid transport of ions and electrons. The high performance would enable the presented NiMn2O4@rGO nanocomposite a promising anode candidate for practical applications in Li-ion batteries.

Multivariate analysis and geochemical approach for assessment of metal pollution state in sediment cores.

PubMed

Jamshidi-Zanjani, Ahmad; Saeedi, Mohsen

2017-07-01

Vertical distribution of metals (Cu, Zn, Cr, Fe, Mn, Pb, Ni, Cd, and Li) in four sediment core samples (C 1 , C 2 , C 3 , and C 4 ) from Anzali international wetland located southwest of the Caspian Sea was examined. Background concentration of each metal was calculated according to different statistical approaches. The results of multivariate statistical analysis showed that Fe and Mn might have significant role in the fate of Ni and Zn in sediment core samples. Different sediment quality indexes were utilized to assess metal pollution in sediment cores. Moreover, a new sediment quality index named aggregative toxicity index (ATI) based on sediment quality guidelines (SQGs) was developed to assess the degree of metal toxicity in an aggregative manner. The increasing pattern of metal pollution and their toxicity degree in upper layers of core samples indicated increasing effects of anthropogenic sources in the study area.

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

A study of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions

DOE PAGES

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; ...

2015-01-26

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of Li xMn 1.5Ni 0.5O 4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn 1.5Ni 0.5O 4 (Phase I), Li 0.5Mnmore » 1.5Ni 0.5O 4 (Phase II) and Mn 1.5Ni 0.5O 4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.« less

Identification of strengthening phases in Al-Cu-Li alloy Weldalite (tm) 049

NASA Technical Reports Server (NTRS)

1991-01-01

Microstructure property relationships were determined for a family of ultrahigh strength weldable Al-Cu-Li based alloys referred to as Weldalite (tm) alloys. The highest strength variant of this family, Weldalite 049, has a high Cu/Li wt pct. ratio with a nominal composition of Al-6.3Cu-1.3Li-0.4Ag-0.4Mg-0.14Zr. Increasing the alloy's lithium content above 1.3 wt pct. resulted in a decrease in both yield and ultimate tensile strength. Strength was shown to be strongly dependent on lithium content, with a maximum in strength occurring in the range of about 1.1 to 1.4 wt pct. lithium. The strengthening phases present in Weldalite 049 (1.3Li) and an Al-6.3Cu-1.9Li-0.4Mg-0.14Zr alloy were identified using transmission electron microscopy (TEM).

Kinetics and structural changes of Li-rich layered oxide 0.5Li2MnO3·0.5LiNi(0.292)Co(0.375)Mn(0.333)O2 material investigated by a novel technique combining in situ XRD and a multipotential step.

PubMed

Shen, Chong-Heng; Huang, Ling; Lin, Zhou; Shen, Shou-Yu; Wang, Qin; Su, Hang; Fu, Fang; Zheng, Xiao-Mei

2014-08-13

Li-rich layered oxide 0.5Li2MnO3·0.5LiNi0.292Co0.375Mn0.333O2 was prepared by an aqueous solution-evaporation route. X-ray powder diffraction (XRD) showed that the as-synthesized material was a solid solution consisting of layered α-NaFeO2-type LiMO2 (M = Ni, Co, Mn) and monoclinic Li2MnO3. The superlattice spots in the selected area electron diffraction pattern indicated the ordering of lithium ions with transition metal (TM) ions in TM layers in this Li-rich layered oxide. Electrochemical performance testing showed that the as-synthesized material could deliver an initial discharge capacity of 267.7 mAh/g, with a capacity retention of 88.5% after 33 cycles. A new combination technique, multipotential step in situ XRD (MPS in situ XRD) measurement, was applied for the first time to investigate the Li-rich layered oxide. Using this approach, the relationships between kinetics and structural variations can be obtained simutaneously. In situ XRD results showed that the c parameter decreased from 3.70 to 4.30 V and increased from 4.30 to 4.70 V, whereas the a parameter underwent a decrease above 4.30 V during the first charge process. Below 3.90 V during the first discharge process, a slight decrease in the c parameter was found along with an increase in the a parameter. During the first charge process, the value of the coefficient of diffusion for lithium ions (DLi+) decreased to its mininum at 4.55 V, which might be associated with Ni(2+) migration, as indicated by both Ni occupancy in 3b sites (Ni3b%) in the Li(+) layers and complicated chemical reactions. Remarkably, a lattice distortion might occur within the local domain in the host stucture during the first discharge process, indicated by a slight splitting of the (003) diffraction peak at 3.20 V.

Metal dynamics in Lake Vanda (Wright Valley, Antarctica)

NASA Technical Reports Server (NTRS)

Green, W. J.; Ferdelman, T. G.; Canfield, D. E.; DeVincenzi, D. L. (Principal Investigator)

1989-01-01

Data are reported for Mn, Fe, Co, Ni, Cu and Cd in the Onyx River, and for Mn, Co, Ni, Cu and Cd in Lake Vanda, a closed-basin Antarctic lake. Oxic water concentrations for Co, Ni, Cu and Cd were quite low and approximate pelagic ocean values. Scavenging of these metals by sinking particles is strongly indicated. Deep-lake profiles reveal a sharp peak in the concentrations of Mn, Fe and Co at the oxic-anoxic boundary at 60 m. Maxima for Ni, Cu and Cd occur higher in the water column, in the vicinity of a Mn submaximum, suggesting early release of these metals from sinking manganese oxide-coated particles. A rough steady-state model leads to the conclusion that there is a large downward flux of Mn into the deep lake and that this flux is sufficient to explain the annual loss of Co, Ni, Cu and Cd. A pronounced geochemical separation between Fe and Mn apparently occurs in this system--Fe being best lost in near-shore environments and Mn being lost in deeper waters. Comparison of metal residence times in Lake Vanda with those in the oceans shows that in both systems Mn, Fe and Co are much more reactive than Ni, Cu and Cd. Energetically favorable inclusion of the more highly charged metals, Mn(IV), Fe(III) and Co(III), into oxide-based lattices is a plausible explanation.

Multi-Functional Surface Engineering for Li-Excess Layered Cathode Material Targeting Excellent Electrochemical and Thermal Safety Properties.

PubMed

Bian, Xiaofei; Fu, Qiang; Pang, Qiang; Gao, Yu; Wei, Yingjin; Zou, Bo; Du, Fei; Chen, Gang

2016-02-10

The Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2 cathode material is modified by a Li4M5O12-like heterostructure and a BiOF surface layer. The interfacial heterostructure triggers the layered-to-Li4M5O12 transformation of the material which is different from the layered-to-LiMn2O4 transformation of the pristine Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. This Li4M5O12-like transformation helps the material to keep high working voltage, long cycle life and excellent rate capability. Mass spectrometry, in situ X-ray diffraction and transmission electron microscope show that the Li4M5O12-like phase prohibits oxygen release from the material bulk at elevated temperatures. In addition, the BiOF coating layer protects the material from harmful side reactions with the electrolyte. These advantages significantly improve the electrochemical performance of Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. The material shows a discharge capacity of 292 mAh g(-1) at 0.2 C with capacity retention of 92% after 100 cycles. Moreover, a high discharge capacity of 78 mAh g(-1) could be obtained at 25 C. The exothermic temperature of the fully charged electrode is elevated from 203 to 261 °C with 50% reduction of the total thermal release, highlighting excellent thermal safety of the material.

Magnetically engineered Cd-free quantum dots as dual-modality probes for fluorescence/magnetic resonance imaging of tumors.

PubMed

Ding, Ke; Jing, Lihong; Liu, Chunyan; Hou, Yi; Gao, Mingyuan

2014-02-01

Magnetically engineered Cd-free CuInS2@ZnS:Mn quantum dots (QDs) were designed, synthesized, and evaluated as potential dual-modality probes for fluorescence and magnetic resonance imaging (MRI) of tumors in vivo. The synthesis of Mn-doped core-shell structured CuInS2@ZnS mainly comprised three steps, i.e., the preparation of fluorescent CuInS2 seeds, the particle surface coating of ZnS, and the Mn-doping of the ZnS shells. Systematic spectroscopy studies were carried out to illustrate the impacts of ZnS coating and the following Mn-doping on the optical properties of the QDs. In combination with conventional fluorescence, fluorescence excitation, and time-resolved fluorescence measurements, the structure of CuInS2@ZnS:Mn QDs prepared under optimized conditions presented a Zn gradient CuInS2 core and a ZnS outer shell, while Mn ions were mainly located in the ZnS shell, which well balanced the optical and magnetic properties of the resultant QDs. For the following in vivo imaging experiments, the hydrophobic CuInS2@ZnS:Mn QDs were transferred into water upon ligand exchange reactions by replacing the 1-dodecanethiol ligand with dihydrolipoic acid-poly(ethylene glycol) (DHLA-PEG) ligand. The MTT assays based on HeLa cells were carried out to evaluate the cytotoxicity of the current Cd-free CuInS2@ZnS:Mn QDs for comparing with that of water soluble CdTe QDs. Further in vivo fluorescence and MR imaging experiments suggested that the PEGylated CuInS2@ZnS:Mn QDs could well target both subcutaneous and intraperitoneal tumors in vivo. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of Mn Nanoparticles on Interfacial Intermetallic Compound Growth in Low-Ag Sn-0.3Ag-0.7Cu- xMn Solder Joints

NASA Astrophysics Data System (ADS)

Tang, Y.; Luo, S. M.; Li, G. Y.; Yang, Z.; Chen, R.; Han, Y.; Hou, C. J.

2018-02-01

Interfacial intermetallic compound (IMC) growth between Cu substrates and low-Ag Sn-0.3Ag-0.7Cu- xMn ( x = 0 wt.%, 0.02 wt.%, 0.05 wt.%, 0.1 wt.%, and 0.15 wt.%) (SAC0307- xMn) solders was investigated under different isothermal aging temperatures of 100°C, 150°C, and 190°C. Scanning electron microscopy (SEM) was employed to observe the microstructural evolution of the solder joints and measure the IMC layer thickness. The IMC phases were identified by energy-dispersive x-ray spectroscopy and x-ray diffraction. The results showed that a Cu6Sn5 IMC layer formed in the as-soldered solder joints, while a duplex structure consisting of a Cu6Sn5 IMC layer near the solder matrix and a Cu3Sn IMC layer was observed after isothermal aging. A considerable drop in the IMC layer thickness was observed when 0.1 wt.% Mn nanoparticles were added. Beyond this amount, the thickness of the IMC layer only slightly increases. Adding Mn nanoparticles can increase the activation energy and thus reduce the interdiffusion rates of the Sn and Cu atoms, which suppresses excessive IMC growth. The solder joint containing 0.1 wt.% Mn nanoparticles has the highest activation energy. SEM images revealed that the number of small particles precipitated in the channels between the Cu6Sn5 IMC layers increases with an increasing proportion of Mn nanoparticles. Based on the microstructural evolution of the solder joints, this study revealed that grain boundary pinning is one of the most important mechanisms for IMC growth inhibition when Mn nanoparticles are added.

Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Wang, F. X.; Xiao, S. Y.; Gao, X. W.; Zhu, Y. S.; Zhang, H. P.; Wu, Y. P.; Holze, R.

2013-11-01

LiMn2O4 spinel was prepared by a hydrothermal method using α-MnO2 nanotubes as precursor at 180 °C, a temperature much lower than that in previously reported methods. It is nanoporous with a pore size of about 40-50 nm and a BET surface area of 9.76 m2 g-1. It exhibits a high specific capacitance of 189 F g-1 at 0.3 A g-1 as a cathode for an aqueous supercapacitor. Even at 12 A g-1, it still has a capacitance of 166 F g-1. After 1500 cycles, there is no evident capacity fading. The LiMn2O4 cathode can deliver an energy density of 31.9 Wh kg-1 at 3480 W kg-1 and even maintain 19.4 Wh kg-1 at about 5100 W kg-1 based on the mass of LiMn2O4.

Synthesis and electrochemical performances of LiNiCuZn oxides as anode and cathode catalyst for low temperature solid oxide fuel cell.

PubMed

Jing, Y; Qin, H; Liu, Q; Singh, M; Zhu, B

2012-06-01

Low temperature solid oxide fuel cell (LTSOFC, 300-600 degrees C) is developed with advantages compared to conventional SOFC (800-1000 degrees C). The electrodes with good catalytic activity, high electronic and ionic conductivity are required to achieve high power output. In this work, a LiNiCuZn oxides as anode and cathode catalyst is prepared by slurry method. The structure and morphology of the prepared LiNiCuZn oxides are characterized by X-ray diffraction and field emission scanning electron microscopy. The LiNiCuZn oxides prepared by slurry method are nano Li0.28Ni0.72O, ZnO and CuO compound. The nano-crystallites are congregated to form ball-shape particles with diameter of 800-1000 nm. The LiNiCuZn oxides electrodes exhibits high ion conductivity and low polarization resistance to hydrogen oxidation reaction and oxygen reduction reaction at low temperature. The LTSOFC using the LiNiCuZn oxides electrodes demonstrates good cell performance of 1000 mW cm(-2) when it operates at 470 degrees C. It is considered that nano-composite would be an effective way to develop catalyst for LTSOFC.

Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4}: Novel keesterite type solid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Vergara, F., E-mail: fer_martina@u.uchile.cl; Galdamez, A., E-mail: agaldamez@uchile.cl; Manriquez, V.

2013-02-15

A new family of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} chalcogenides has been synthesized by conventional solid-state reactions at 850 Degree-Sign C. The reactions products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of two members of the solid solution series Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4} have been determined by single-crystal X-ray diffraction. Both phases crystallize in the tetragonal keesterite-type structure (space group I4{sup Macron }). The distortions of the tetrahedral volume of Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4}more » were calculated and compared with the corresponding differences in the Cu{sub 2}MnSnS{sub 4} (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic. - Graphical abstract: View along [100] of the Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} structure showing tetrahedral units and magnetic measurement ZFC-FC at 500 Oe. The insert shows the 1/{chi}-versus-temperature plot fitted by a Curie-Weiss law. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} solid solutions belong to the family of compounds adamantine. Black-Right-Pointing-Pointer Resolved single crystals of the solid solutions have space group I4{sup Macron }. Black-Right-Pointing-Pointer The distortion of the tetrahedral volume of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} were calculated. Black-Right-Pointing-Pointer These solid solutions are antiferromagnetic.« less

Three-volt lithium-ion battery with Li[Ni 1/2Mn 3/2]O 4 and the zero-strain insertion material of Li[Li 1/3Ti 5/3]O 4

NASA Astrophysics Data System (ADS)

Ariyoshi, Kingo; Yamamoto, Satoshi; Ohzuku, Tsutomu

A 3 V lithium-ion cell with Li[Ni 1/2Mn 3/2]O 4 ( Fd 3¯m ; a=8.17 Å) and the zero-strain insertion material of Li[Li 1/3Ti 5/3]O 4 ( Fd 3¯m ; a=8.36 Å) was examined with an emphasis on rate-capability and cycle life. This cell showed a quite flat operating voltage of 3.2 V with excellent cycleability. Accelerated cycle tests indicated that 83% of the initial capacity was delivered and stored even after 1100 cycles. Although the calculated energy density of a Li[Li 1/3Ti 5/3]O 4/Li[Ni 1/2Mn 3/2]O 4 cell was about 250 Wh kg -1 or 1000 Wh dm -3 based on the active material weight or volume, the 3 V lithium-ion battery exhibited positive characteristic features, such as flatness in operating voltage, high rate capability, and cycle life.

A discrete Cu cluster and a 3D MnII-CuII framework based on assembly of Mn2Cu4 clusters: synthesis, structure and magnetic properties.

PubMed

Chakraborty, Anindita; Escuer, Albert; Ribas, Joan; Maji, Tapas Kumar

2016-10-04

The synthesis, single-crystal structure characterization and detailed magnetic study of a homometallic hexanuclear Cu II cluster [Cu 6 (μ 3 -OH) 2 (ppk) 6 (H 2 O) 2 (NO 3 ) 4 ] (1) and a three-dimensional (3D) compound [{MnCu 2 (dpkO 2 H) 2 (dpkO 2 )N 3 }·(NO 3 )·H 2 O] n (2) (ppk = phenyl-2-pyridyl ketoxime; dpk = di-2-pyridyl ketone) consisting of heterometallic Mn II -Cu II hexanuclear cores as secondary building units are reported in this paper. In compound 1, two symmetry-related Cu 3 triangles consisting of a hydroxido-bridged trinuclear unit, [Cu 3 (μ 3 -OH)(ppk) 3 (H 2 O)(NO 3 )] + , are assembled through nitrate bridging giving rise to the homometallic Cu 6 cluster. Compound 2 contains heterometallic {MnCu} cores, which are further connected to each other through an azido bridging ligand in all the crystallographic directions, resulting in a 3D metal-organic framework. Construction of such a heterometallic 3D framework from {MnCu} units is until now, unknown. Magnetic studies of both 1 and 2 were performed in detail and both compounds show dominant antiferromagnetic interaction in the respective clusters. Compound 1 reveals significant spin frustration and anti-symmetric exchange interaction in the trinuclear cores, with a significantly high value of J av (-655 cm -1 ). Furthermore, compound 2 exhibits a dominant antiferromagnetic interaction, which is also supported by an extensive magneto-structural correlation which considers the different magnetic pathways.

Thermal-stability studies of electrode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Jiang, Junwei

2005-07-01

The thermal stability of lithium-ion batteries has recently attracted attention for two major reasons. (1) Attempts to make large-size cells used in power tools, E-bikes and EVs. Large cells have lower surface area to volume ratios and hence heat dissipation is more problematic than 18650-size cells. Safety problems, therefore, for large cells are more serious. (2) Next generation high-capacity electrodes will increase the energy density of lithium-ion cells meaning even an 18650-size cell may face safety concerns. This thesis presents studies of the thermal stability of electrode materials in electrolytes to understand their reactivity. A search for new positive electrode materials with high thermal stability was made. The thermal stability of two common electrode materials (Li0.81 C6 and Li0.5CoO2) in lithium-ion cells was studied by Accelerating Rate Calorimeter (ARC). Li0.81C 6 has much lower reactivity with lithium bis(oxalato)borate (LiBOB) electrolyte compared to LiPF6 electrolyte. It is not the case, however, for Li0.5CoO2. Oven tests of full LiCoO 2/C 18650-size cells with LiBOB or LiPF6 electrolytes, confirmed the ARC results. ARC was then used to study the reactivity of existing electrode materials. The thermal stability of a negative electrode material was found to increase with the binding energy of Li atoms hosted in the material. Li0.5VO 2 (B) has a higher lithium binding energy (2.45 eV vs. Li) than Li 0.81C6 (0.1 eV vs. Li) and Li7Ti5O 12 (1.55 eV) and it shows the highest thermal stability in EC/DEC among the three materials. The reactivity of two existing positive electrode materials, LiMn2O4 and LiFePO4, was studied. Cell systems expected to be highly tolerant to thermal abuse were suggested: LiFePO 4/C or Li4Ti5O12 in LiBOB electrolytes. The system, x Li[Ni1/2Mn1/2]O2 • y LiCoO2 • z Li[Li1/3Mn2/3]O2 (x + y + z = 1), was explored for new positive electrode materials with large capacity and high thermal stability. Li[(Ni0.5Mn0.5) xCo1-x]O2 (0.4 ≤ x ≤ 0.7) samples have excellent electrochemical properties and thermal stability and are being commercialized by industry. Li[(Ni0.5Mn0.5)xCo y(Li1/3Mn2/3)z]O2 (1/12 ≤ y ≤ 1/4, 1/6 ≤ z ≤ 1/3) samples have high specific capacity (200 mA h g-1), excellent cycling performance, and are safer than LiCoO2. The materials are suggested for energy cells used in cell phones, laptops, and so on.

The influence of liming on soil chemical properties and on the alleviation of manganese and copper toxicity in Juglans regia, Robinia pseudoacacia, Eucalyptus sp. and Populus sp. plantations.

PubMed

Chatzistathis, T; Alifragis, D; Papaioannou, A

2015-03-01

Juglans regia, Robinia pseudoacacia, Eucalyptus sp. and Populus sp. plantations, suffering from Mn and Cu toxicity, were limed in order to reduce Cu and Mn solubility in soil. The purposes of the present work were: i) to study the changes in soil chemical properties after the addition of CaCO3, ii) to investigate the influence of liming on the reduction of Mn and Cu toxicity. After the addition of CaCO3 (three applications, during three successive years), pH and CaCO3 content were significantly increased, while organic C and N were significantly reduced. Exchangeable Ca concentrations have been slightly, or significantly, increased, while those of Mg have been decreased; in addition, ratios Ca/Mg and C/N have been significantly increased after liming. Impressive reductions of DTPA extractable Cu and Mn concentrations (more than 10 times in most cases) were recorded. It was also found that trees without Mn and Cu toxicity symptoms (healthy tress) before liming did not have, in many cases, significantly greater leaf Mn, Cu and Fe concentrations, than trees after soil liming (all the trees were healthy). This probably happened because excess Mn and Cu quantities had been accumulated into their root system. Finally, leaf Mn, Cu and Zn concentrations of trees suffering from toxicity were significantly decreased after soil liming, while leaf Fe concentrations, in all the plant species studied, were increased. Copyright © 2014 Elsevier Ltd. All rights reserved.

Relative contribution of CTR1 and DMT1 in copper transport by the blood–CSF barrier: Implication in manganese-induced neurotoxicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Gang; Department of Occupational and Environmental Health and the Ministry of Education Key Lab of Hazard Assessment and Control in Special Operational Environment, School of Public Health, Fourth Military Medical University, Xi'an, Shanxi 710032; Chen, Jingyuan

2012-05-01

The homeostasis of copper (Cu) in the cerebrospinal fluid (CSF) is partially regulated by the Cu transporter-1 (CTR1) and divalent metal transporter-1 (DMT1) at the blood–CSF barrier (BCB) in the choroid plexus. Data from human and animal studies suggest an increased Cu concentration in blood, CSF, and brains following in vivo manganese (Mn) exposure. This study was designed to investigate the relative role of CTR1 and DMT1 in Cu transport under normal or Mn-exposed conditions using an immortalized choroidal Z310 cell line. Mn exposure in vitro resulted in an increased cellular {sup 64}Cu uptake and the up-regulation of both CTR1more » and DMT1. Knocking down CTR1 by siRNA counteracted the Mn-induced increase of {sup 64}Cu uptake, while knocking down DMT1 siRNA resulted in an increased cellular {sup 64}Cu uptake in Mn-exposed cells. To distinguish the roles of CTR1 and DMT1 in Cu transport, the Z310 cell-based tetracycline (Tet)-inducible CTR1 and DMT1 expression cell lines were developed, namely iZCTR1 and iZDMT1 cells, respectively. In iZCTR1 cells, Tet induction led to a robust increase (25 fold) of {sup 64}Cu uptake with the time course corresponding to the increased CTR1. Induction of DMT1 by Tet in iZDMT1 cells, however, resulted in only a slight increase of {sup 64}Cu uptake in contrast to a substantial increase in DMT1 mRNA and protein expression. These data indicate that CTR1, but not DMT1, plays an essential role in transporting Cu by the BCB in the choroid plexus. Mn-induced cellular overload of Cu at the BCB is due, primarily, to Mn-induced over-expression of CTR1. -- Highlights: ► This study compares the relative role of CTR1 and DMT1 in Cu transport by the BCB. ► Two novel tetracycline-inducible CTR1 and DMT1 expression cell lines are created. ► CTR1, but not DMT1, plays an essential role in transporting Cu by the BCB. ► Mn-induced cellular Cu overload is due to its induction of CTR1 rather than DMT1. ► Induction of CTR1 by Mn in the BCB contributes to an elevated Cu level in the CSF.« less

Observation of self-regulating response in Li xM yMn 2-yO 4 (M=Mn, Ni): A study using density functional theory

NASA Astrophysics Data System (ADS)

Ragavendran, K.; Sherwood, Daniel; Emmanuel, Bosco

2009-02-01

Density functional theory is used to understand the response of the transition metal-oxygen octahedra in Li xMn 2O 4 and Li xNi 0.5Mn 1.5O 4 to lithium intercalation and de-intercalation. Electronic structure computations on these compounds for x=0, 0.5 and 1 indicate that the 3d DOS of Mn is almost unaffected to variations in x. On the other hand, the oxygen 2p-DOS and to a lesser extent Ni 3d DOS are found to be sensitive to perturbation. The observations are explained on the grounds of self-regulating response, characteristic of systems having localized d states that communicate with a covalent manifold.

Organic-Acid-Assisted Fabrication of Low-Cost Li-Rich Cathode Material (Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2) for Lithium-Ion Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Taolin; Chen, Shi; Li, Li

2014-12-24

A novel Li-rich cathode Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2 (0.4Li(2)MnO(3-)0.6LiFe(1/3)Ni(1/3)Mn(1/3)O(2)) was synthesized by a solgel method, which uses citric acid (SC), tartaric acid (ST), or adipic acid (SA) as a chelating agent. The structural, morphological, and electrochemical properties of the prepared samples were characterized by various methods. X-ray diffraction showed that single-phase materials are formed mainly with typical alpha-NaFeO2 layered structure (R3 m), and the SC sample has the lowest Li/Ni cation disorder. The morphological study indicated homogeneous primary particles in good distribution size (100 nm) with small aggregates. The Fe, Ni, and Mn valences were determined by X-ray absorption near-edge structure analysis. Inmore » coin cell tests, the initial reversible discharge capacity of an SA electrode was 289.7 mAh g(-1) at the 0.1C rate in the 1.54.8 V voltage range, while an SC electrode showed a better cycling stability with relatively high capacity retention. At the 2C rate, the SC electrode can deliver a discharge capacity of 150 mAh g(-1) after 50 cycles. Differential capacity vs voltage curves were employed to further investigate the electrochemical reactions and the structural change process during cycling. This low-cost, Fe-based compound prepared by the solgel method has the potential to be used as the high capacity cathode material for Liion batteries.« less

Improving low-temperature performance of spinel LiNi0.5Mn1.5O4 electrode and LiNi0.5Mn1.5O4/Li4Ti5O12 full-cell by coating solid-state electrolyte Li-Al-Ti-P-O

NASA Astrophysics Data System (ADS)

Bi, Kun; Zhao, Shi-Xi; Huang, Chao; Nan, Ce-Wen

2018-06-01

Octahedral cathode materials LiNi0.5Mn1.5O4 (LNMO), with primary particles size of 300-600 nm are prepared through one-step co-precipitation. Then solid-state electrolyte Li2O-Al2O3-TiO2-P2O5 (LATP) was coated on LNMO to form continuous surface-modification layer. There is no obviously difference of structure, morphology between coated LATP LiNi0.5Mn1.5O4 (LATP-LNMO) and pristine LiNi0.5Mn1.5O4 (P-LNMO). Low-temperature electrochemical performance of P-LNMO and LATP-LNMO electrodes, including charge-discharge capacity, cycle performance, middle discharge voltage and electrochemical impedance spectra (EIS), were measured systematically with three electrode. The results reveal that LATP-LNMO electrode presents superior electrochemical performance at low temperature, compared to P-LNMO electrode. At -20 °C, the capacity retention of LATP-LNMO (61%) is much higher than that of P-LNMO (39%). According to EIS, the enhancement of performance of LATP-LNMO cathode at low temperature can be attribute to LATP coating, which not only promotes lithium-ion diffusion at electrode/electrolyte interface but also decreases the charge transfer resistance. Finally, the electrochemical performances of full cell of LATP-LNMO or P-LNMO cathode vs Li4Ti5O12 anode are investigated. The energy density can be achieved to 270 Wh·Kg-1 at -20 °C if using LATP-LNMO, which is much better than that of P-LNMO.

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

PubMed

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

2017-02-08

We demonstrate herein that Mn 3+ and not Mn 2+ , as commonly accepted, is the dominant dissolved manganese cation in LiPF 6 -based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn 3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn 3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn 3+ occurs at a very slow rate.

An insight into the influence of crystallite size on the performances of microsized spherical Li(Ni0.5Co0.2Mn0.3)O2 cathode material composed of aggregated nanosized particles

NASA Astrophysics Data System (ADS)

Fan, Guangxin; Wen, Yin; Liu, Baozhong; Yang, Wenpeng

2018-02-01

Relationships between the performance and the crystallite size of the microsized spherical Li(Ni0.5Co0.2Mn0.3)O2 cathode material composed of aggregated nanosized primary particles have been comprehensively studied. The cathode material was synthesized by a high-temperature solid-state method. The results obtained by XRD, Rietveld refinement, SEM, HR-TEM, DSC, and galvanostatic test show that the crystallite size (XS) of Li(Ni0.5Co0.2Mn0.3)O2 is greatly affected by the temperature in the range of 750 to 820 °C. Most of all, the crystallite size plays a unique role in the performance of the material. That is, the electrochemical characteristics of Li(Ni0.5Co0.2Mn0.3)O2, such as discharge capacity, rate performance, and thermal stability, are closely related to the crystallite size. Furthermore, the retention of discharge capacity is determined by that of crystallite size in Li(Ni0.5Co0.2Mn0.3)O2 after 100 cycles.

Studies on Electronic Structure and Magnetic Properties of an Organic Magnet with Metallic Mn2+ and Cu2+ Ions

NASA Astrophysics Data System (ADS)

Yao, Jian-Guo; Peng, Guang-Xiong

2004-11-01

The electronic structure and the magnetic properties of the non-pure organic ferromagnetic compound MnCu(pbaOH)(H2O)3 with pbaOH = 2-hydroxy-1, 3-propylenebis (oxamato) are studied by using the density-functional theory with local-spin-density approximation. The density of states, total energy, and the spin magnetic moment are calculated. The calculations reveal that the compound MnCu(pbaOH)(H20)3 has a stable metal-ferromagnetic ground state, and the spin magnetic moment per molecule is 2.208 μB, and the spin magnetic moment is mainly from Mn ion and Cu ion. An antiferromagnetic order is expected and the antiferromagnetic exchange interaction of d-electrons of Cu and Mn passes through the antiferromagnetic interaction between the adjacent C, O, and N atoms along the path linking the atoms Cu and Mn. The project supported by National Natural Science Foundation of China under Grant No. 10375074 and Hubei Automotive Industries Institute Foundation under Grant No. QY2002-16

CONSTITUTIVE BEHAVIOR OF AS-QUENCHED Al-Cu-Mn ALLOY

NASA Astrophysics Data System (ADS)

Yang, Xia-Wei; Zhu, Jing-Chuan; Nong, Zhi-Sheng; Ye, Mao; Lai, Zhong-Hong; Liu, Yong

2013-07-01

The hot flow stress of as-quenched Al-Cu-Mn alloy was modeled using the constitutive equations. The as-quenched Al-Cu-Mn alloy were treated with isothermal hot compression tests in the temperature range of 350-500°C, the strain rate range of 0.001-1 s-1. The hyperbolic sine equation was found to be appropriate for flow stress modeling and prediction. Based on the hyperbolic sine equation, a constitutive equation is a relation between 0.2 pct yield stress and deformation conditions (strain rate and deformation temperature) was established. The corresponding hot deformation activation energy (Q) for as-quenched Al-Cu-Mn alloy was determined to be 251.314 kJ/mol. Parameters of constitutive equation of as-quenched Al-Cu-Mn alloy were calculated at different small strains (≤ 0.01). The calculated flow stresses from the constitutive equation are in good agreement with the experimental results. Therefore, this constitutive equation can be used as an accurate temperature-stress model to solve the problems of quench distortion of Al-Cu-Mn alloy parts.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Effect of dopants on the TL response of the new LiF:Mg,Cu,Ag material

NASA Astrophysics Data System (ADS)

Yahyaabadi, A.; Torkzadeh, F.; Rezaei-Ochbelagh, D.; Hosseini Pooya, M.

2018-07-01

The new TL LiF:Mg,Cu,Ag material was prepared and investigated in this study. The TL intensity of LiF:Mg,Cu,Ag is strongly dependent on the concentration of dopants and the preparation procedure. Any small change in these factors can cause alterations in TL response. In this study, the influence of Cu and Ag concentrations on the response of the LiF:Mg,Cu,Ag sample was investigated and showed that the height of the low, main and high temperature peaks changes with Ag concentration. Their intensities increased with increasing Ag concentration to a maximum value and decreased with higher Ag concentration. It was also found that Cu concentration less than 0.05 mol% influences the maximum peak height and TL intensity. The optimum Cu and Ag concentrations were found to be 0.05 and 0.1 mol% at 1005 °C QT, respectively. The role of dopants in LiF:Mg,Cu,Ag material was also investigated. The results showed that presence of three dopants is important for having material with sensitivity higher than LiF:Mg,Ti. The Mg dopant plays a crucial role in the formation of the trapping center and the position of the main dosimetric peak.

Purification and characterization of two novel peroxidases from the dye-decolorizing fungus Bjerkandera adusta strain CX-9.

PubMed

Bouacem, Khelifa; Rekik, Hatem; Jaouadi, Nadia Zaraî; Zenati, Bilal; Kourdali, Sidali; El Hattab, Mohamed; Badis, Abdelmalek; Annane, Rachid; Bejar, Samir; Hacene, Hocine; Bouanane-Darenfed, Amel; Jaouadi, Bassem

2018-01-01

Two extracellular peroxidases from Bjerkandera adusta strain CX-9, namely a lignin peroxidase (called LiP BA45) and manganese peroxidase (called MnP BA30), were purified simultaneously by applying successively, ammonium sulfate precipitation-dialysis, Mono-S Sepharose anion-exchange and Sephacryl S-200 gel filtration and biochemically characterized. The sequence of their NH 2 -terminal amino acid residues showed high homology with those of fungi peroxidases. Matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF/MS) analysis revealed that the purified enzymes MnP BA30 and LiP BA45 were a monomers with a molecular masses 30125.16 and 45221.10Da, respectively. While MnP BA30 was optimally active at pH 3 and 70°C, LiP BA45 showed optimum activity at pH 4 and 50°C. The two enzymes were inhibited by sodium azide and potassium cyanide, suggesting the presence of heme-components in their tertiary structures. The K m and V max for LiP BA45 toward 2,4-Dichlorolphenol (2,4-DCP) were 0.099mM and 9.12U/mg, respectively and for MnP BA30 toward 2,6-Dimethylphenol (2,6-DMP), they were 0.151mM and 18.60U/mg, respectively. Interestingly, MnP BA30 and LiP BA45 demonstrated higher catalytic efficiency than that of other tested peroxidases (MnP, LiP, HaP4, and LiP-SN) and marked organic solvent-stability and dye-decolorization efficiency. Data suggest that these peroxidases may be considered as potential candidates for future applications in distaining synthetic-dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

V-insertion in Li(Fe,Mn)FePO4

NASA Astrophysics Data System (ADS)

Wu, T.; Liu, J.; Sun, L.; Cong, L.; Xie, H.; Abdel-Ghany, A.; Mauger, A.; Julien, C. M.

2018-04-01

Insertion of 3% vanadium in LiMn1-yFeyPO4 has been investigated, with y = 0.2 corresponding to the highest manganese concentration before the stress/strain field degrades the electrochemical performance. V substitutes for Fe2+ in the trivalent state V3+. This substitution is accompanied with the formation of Fe vacancies while Mn remains in the Mn2+ valence state, leading to a composition LiMn0.8Fe0.2-0.045V0.03□0.015PO4 where □ is a Fe vacancy. The comparison between electrochemical properties of a pristine sample and a sample with 3 mol.% vanadium made of particles with the same morphology (spherical particles with the same dispersion 100-150 nm in size) and same carbon coating (same conductivity of the carbon layer) is reported. Although the vanadium is in the V3+ state at open circuit voltage (2.6 V) before cycling, a reversible V3+/V2+ is observed when the potential of the half-cell is lowered below the redox potential of 1.8 V vs Li+/Li, due to Li-vacancies. The V-insertion improves the electrochemical properties, due to a synergetic effect of an increase of the lithium diffusion coefficient by a factor two and an increase of the electric conductivity at any Li-concentration during the cycling process, in contradiction with prior claims that attributed the increase of conductivity to V-based impurities.

A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li1.2Ni0.13M0.13Mn0.54O2 where M = Fe or Co

NASA Astrophysics Data System (ADS)

Laisa, C. P.; Nanda Kumar, A. K.; Selva Chandrasekaran, S.; Murugan, P.; Lakshminarasimhan, N.; Govindaraj, R.; Ramesha, K.

2016-08-01

In this work we compare electrochemical cycling stability of Fe containing Li rich phase Li1.2Ni0.13Fe0.13Mn0.54O2 (Fe-Li rich) with the well-known Co containing Li rich composition Li1.2Ni0.13Co0.13Mn0.54O2 (Co-Li rich). During the first charge, the activation plateau corresponding to removal of Li2O from the structure is smaller (removal of 0.6 Li) in the case of Fe-Li rich compared to Co-Li rich composition (0.8 Li removal). Consequently, the Fe compound shows better capacity retention; for example, after 100 cycles Fe-Li rich compound exhibits 20% capacity degradation where as it is about 40% in the case of Co-Li rich phase. The electrochemical and microscopy studies support the fact that compared to Co-Li rich compound, the Fe-Li rich composition display smaller voltage decay and reduced spinel conversion. XPS studies on charged/discharged Fe-Li rich samples show participation of Fe+3/Fe+4 redox during electrochemical cycling which is further supported by our first principles calculations. Also the temperature dependent magnetic studies on charge-discharged samples of Fe-Li rich compound point out that magnetic behavior is sensitive to cation oxidation states and Ni/Li disorder.

Surface characterization of ZnO/ZnMn{sub 2}O{sub 4} and Cu/Mn{sub 3}O{sub 4} powders obtained by thermal degradation of heterobimetallic complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barrault, Joeel, E-mail: joel.barrault@univ-poitiers.fr; Makhankova, Valeriya G., E-mail: leram@univ.kiev.ua; Khavryuchenko, Oleksiy V.

2012-03-15

From the selective transformation of the heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes with 2,2 Prime -bipyridyl by thermal degradation at relatively low (350 Degree-Sign C) temperature, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Morphology of the powder surface was examined by scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Surface composition was determined by X-ray photoelectron spectroscopy (XPS). Specific surface of the powders by nitrogen adsorption was found to be 33{+-}0.2 and 9{+-}0.06more » m{sup 2} g{sup -1} for Zn-Mn and Cu-Mn samples, respectively, which is comparable to those of commercial products. - Graphical abstract: From the selective transformation of heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes, it was possible to get either well defined spinel ZnMn{sub 2}O{sub 4} over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn{sub 3}O{sub 4}) in a core-shell like structure. Highlights: Black-Right-Pointing-Pointer Thermal degradation of heterometallic complexes results in fine disperse particles. Black-Right-Pointing-Pointer Core-shell Cu/Mn{sub 3}O{sub 4} particles are obtained. Black-Right-Pointing-Pointer ZnMn{sub 2}O{sub 4} spinel layer covers ZnO particles.« less

Hydrothermal synthesis of cathode materials

NASA Astrophysics Data System (ADS)

Chen, Jiajun; Wang, Shijun; Whittingham, M. Stanley

A number of cathodes are being considered for the next generation of lithium ion batteries to replace the expensive LiCoO 2 presently used. Besides the layered oxides, such as LiNi yMn yCo 1-2 yO 2, a leading candidate is lithium iron phosphate with the olivine structure. Although this material is inherently low cost, a manufacturing process that produces electrochemically active LiFePO 4 at a low cost is also required. Hydrothermal reactions are one such possibility. A number of pure phosphates have been prepared using this technique, including LiFePO 4, LiMnPO 4 and LiCoPO 4; this method has also successfully produced mixed metal phosphates, such as LiFe 0.33Mn 0.33Co 0.33PO 4. Ascorbic acid was found to be better than hydrazine or sugar at preventing the formation of ferric ions in aqueous media. When conductive carbons are added to the reaction medium excellent electrochemical behavior is observed.

Fluorescence turn-on detection of alkaline phosphatase activity based on controlled release of PEI-capped Cu nanoclusters from MnO2 nanosheets.

PubMed

Zhang, Yunyi; Li, Yongxin; Zhang, Cuiyun; Zhang, Qingfeng; Huang, Xinan; Yang, Meiding; Shahzad, Sohail Anjum; Lo, Kenneth Kam-Wing; Yu, Cong; Jiang, Shichun

2017-08-01

A fluorescence turn-on assay for alkaline phosphatase (ALP) activity is developed through the controlled release of polyethyleneimine-capped copper nanoclusters (PEI-capped CuNCs) from the MnO 2 nanosheets. In an aqueous solution, the positively charged PEI-capped CuNCs could be adsorbed onto the surface of the negatively charged MnO 2 nanosheets. Such adsorption through favorable electrostatic interactions could efficiently quench the nanocluster fluorescence emission via resonance energy transfer from the PEI-capped CuNCs to the MnO 2 nanosheets. 2-Phospho-L-ascorbic acid (AAP) could be hydrolyzed to L-ascorbic acid (AA) in the presence of ALP. AA could reduce MnO 2 into Mn 2+ and trigger the disintegration of the MnO 2 nanosheets. As a result, the CuNCs were released and the quenched fluorescence was recovered efficiently. The detection strategy is simple, inexpensive, sensitive, selective, with low toxicity, and has better biocompatibility. The newly fabricated biosensor for ALP activity will potentially make it a robust candidate for numerous biological and biomedical applications.

Catalytic removal of phenol from gas streams by perovskite-type catalysts.

PubMed

Chen, Dai Ling; Pan, Kuan Lun; Chang, Moo Been

2017-06-01

Three perovskite-type catalysts prepared by citric acid method are applied to remove phenol from gas streams with the total flow rate of 300mL/min, corresponding to a GHSV of 10,000/hr. LaMnO 3 catalyst is first prepared and further partially substituted with Sr and Cu to prepare La 0.8 Sr 0.2 MnO 3 and La 0.8 Sr 0.2 Mn 0.8 Cu 0.2 O 3 , and catalytic activities and fundamental characteristics of these three catalysts are compared. The results show that phenol removal efficiency achieved with La 0.8 Sr 0.2 Mn 0.8 Cu 0.2 O 3 reaches 100% with the operating temperature of 200°C and the rate of mineralization at 300°C is up to 100%, while the phenol removal efficiencies achieved with La 0.8 Sr 0.2 MnO 3 and LaMnO 3 are up to 100% with the operating temperature of 300°C and 400°C, respectively. X-ray photoelectron spectroscopy (XPS) analysis shows that the addition of Sr and Cu increases the lattice oxygen of La 0.8 Sr 0.2 Mn 0.8 Cu 0.2 O 3 , and further increases mobility or availability of lattice oxygen. The results indicate that La 0.8 Sr 0.2 Mn 0.8 Cu 0.2 O 3 has the best activity for phenol removal among three catalysts prepared and the catalytic activity of phenol oxidation is enhanced by the introduction of Sr and Cu into LaMnO 3 . Apparent activation energy of 48kJ/mol is calculated by Mars-Van Krevelen Model for phenol oxidation with La 0.8 Sr 0.2 Mn 0.8 Cu 0.2 O 3 as catalyst. Copyright © 2016. Published by Elsevier B.V.

X-ray diffraction analysis of LiCu2O2 crystals with additives of silver atoms

NASA Astrophysics Data System (ADS)

Sirotinkin, V. P.; Bush, A. A.; Kamentsev, K. E.; Dau, H. S.; Yakovlev, K. A.; Tishchenko, E. A.

2015-09-01

Silver-containing LiCu2O2 crystals up to 4 × 8 × 8 mm in size were grown by the crystallization of 80(1- x)CuO · 20 x AgNO3 · 20Li2CO3 (0 ≤ х ≤ 0.5) mixture melt. According to the X-ray spectral and Rietveld X-ray diffraction data, the maximum amount of silver incorporated in the LiCu2O2 structure is about 4 at % relative to the copper content. It was established that silver atoms occupy statistically crystallographic positions of lithium atoms. The incorporation of silver atoms is accompanied by a noticeable increase in parameter с of the LiCu2O2 rhombic unit cell, a slight increase in parameter а, and a slight decrease in parameter b.

Crystal habit-tuned nanoplate material of Li[Li1/3-2x/3NixMn2/3-x/3]O₂ for high-rate performance lithium-ion batteries.

PubMed

Wei, Guo-Zhen; Lu, Xia; Ke, Fu-Sheng; Huang, Ling; Li, Jun-Tao; Wang, Zhao-Xiang; Zhou, Zhi-You; Sun, Shi-Gang

2010-10-15

A cathode for high-rate performance lithium-ion batteries (LIBs) has been developed from a crystal habit-tuned nanoplate Li(Li(0.17)Ni(0.25)Mn(0.58))O₂ material, in which the proportion of (010) nanoplates (see figure) has been significantly increased. The results demonstrate that the fraction of the surface that is electrochemically active for Li(+) transportation is a key criterion for evaluating the different nanostructures of potential LIB materials.

The geochemical characteristics of soils of vineyards and tea gardens before and after their use in the South of Russia

NASA Astrophysics Data System (ADS)

Alekseenko, Vladimir; Alekseenko, Alexey; Vlasova, Elena; Voronets, Svetlana

2013-04-01

The concentrations of 25 chemical elements in the forest soils, where formerly the vineyards and tea gardens were cultivated, and in the soils of functioning and abandoned 5, 10, 25, 30 and 50 years ago vineyards and tea gardens were considered. The loss and accumulation of elements were studied in the top-horizon (30 centimeters) during the human impact and after its ending. All the data are given with the probability of 95 %. The analyses of more than 1000 samples were used. Comparing to the forest soils, in the tea gardens soils has accumulated P (+702) and leached away Ge (-0.36), Yb (-0.54), Be (-0.84), Ba (-114) (in the gapes - concentration, tons per square kilometer). The leaching of row of elements has continued in the soils of abandoned plantations comparing to the forest soils with some changes in intensity; besides the accumulation of Mn (+318) and Ti (+804) had been occurred during the last 50 years. Comparing to the contemporary plantations in the soils of abandoned ones had been taken place the accumulation of elements during the last 50 years. Its maximum had manifested after 30 years: Mn (366) > Zn (34.8) > V (28.2) > Ni (6.6) > Ga (1.8) > Sn (0.4). The loss was detected for P. The intensity of all considered processes of loss and accumulation was spasmodic changing in the different time periods. During the last 50 years ecology-geochemical "recovery" of abandoned tea gardens soil has not happened. In the functioning vineyards soils, comparing to the initial forest soils has raised the concentrations of Cu (+16.1) and P (+96); declined - Bi (-0.12), Mo (-0.4), Co (-3), Ga (-4.3), Pb (-5.3), Li (-5.5), Mn (-126) and Ti (-684). In the soils of abandoned vineyards, comparing to the forest soils, during the last 25 years had been taken place accumulation of Mo (+0.7), Cr (+29.4), Cu (+50.3) and leaching away Co (-1.8), Ga (-3.7), Ni (-4.2), Li (-7.4). In the soils of abandoned vineyards, comparing to the functioning ones, during the last 25 years had been taken place accumulation of Bi, Mn, Cr, Mo, Cu. The most intensive accumulation of Pb, Ga and Ti was found in the soils of vineyards, which were abandoned 5 years ago. As can be seen from the above, the creation of tea gardens and vineyards has changed the geochemical characteristics of soils in the region. The processes of elements loss and accumulation continue after the end of landscapes exploitation, and they have not returned to the initial conditions for the last 25-50 years.

Effects of cycling temperatures on the voltage fade phenomenon in 0.5Li 2 MnO 3 ·0.5LiNi 0.375 Mn 0.375 Co 0.25 O 2 cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vu, Anh; Walker, Lee K.; Bareño, Javier

2015-04-01

The rate of voltage fade in 0.5Li2MnO3•0.5LiNi0.375Mn0.375Co0.25O2 cathodes was measured in half-cells in a temperature range of 25 to 55°C. On the basis of the dependence of the values of the open-circuit potential with cycle count and temperature, the voltage fade phenomenon seems to consist of two chemical processes: one that can be described using a parabolic rate law and another that uses a linear-with-time law. As the cycling temperature increased, the relative contributions of the two processes changed. On the basis of the overall rate versus temperature data, we believe the two processes may be in competition with onemore » another.« less

Investigation into key interfacial reactions within lithium-ion batteries

NASA Astrophysics Data System (ADS)

Vissers, Daniel Richard

Given the concern of global climate change and the understanding that carbon dioxide emissions are driving this change, much effort has been invested into lowering carbon dioxide emissions. One approach to reduce carbon dioxide emissions is to curtail the carbon dioxide emissions from vehicles through the introduction of hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. Today, lithium cobalt oxide materials are widely used in consumer electronic applications, yet these materials are cost prohibitive for larger scale vehicle applications. As a result, alternative materials with higher energy densities and lower costs are being investigated. One key alternative to cobalt that has received much attention is manganese. Manganese is of interest for its lower cost and favorable environmental friendliness. The use of manganese has led to numerous cathode materials such as Li 1-deltaMn2O4 (4V spinel), Li1-deltaMn 1.5Ni0.25O4 (5V spinel), Li1-(Mn 1-x-yNiyCox)O2 (layered), Li2MnO 3-Li1-delta(Mn1-x-yNiyCox)O 2 (layered-layered), and Li2MnO3-Li1-delta (Mn1-x-yNiyCox)1O2 -Li1-deltaMn2O4 (layered-layered-spinel). The work disclosed in the dissertation focuses on two topics associated with these manganese based cathodes. The first topic is the exceptional cyclic-ability of a high power, high energy density, 5V spinel cathode material (Li 1-deltaMn1.5Ni0.25O4) with a core-shell architecture, and the second is the severe capacity fade associated with manganese dissolution from cathodes at elevated operating temperatures. Both topics are of interest to the Li-ion battery industry. For instance, a 5V spinel cathode represents a viable path to increase both the power and energy density of Li-ion batteries. As its name implies, the 5V spinel operates at 5V that is higher than the conventional 4V lithium ion batteries. Since power and energy are directly proportional to the potential, moving from an operating potential of 4V to 5V represents an increase in both power and energy densities of 25%. When the 5V spinel cathode is coupled with a graphite anode, an energy density of up to 240 Wh kg-1 is possible [2]. Secondly, the severe capacity fade associated with the manganese dissolution generally leads to a design with oversized battery packs, like those for the General Motors Chevy Volt, to meet warranty requirements. The result of this work led to deeper understandings of the underlying mechanisms for the exceptional cyclic-ability of the core-shell 5V spinel and for the severe capacity fade associated with manganese dissolution from the cathode and to a rational approach to resolve the severe capacity fade associated with manganese dissolution.

Magnetic characteristics of a new cubic defect spinel Li0.5Mg0.5MnO3

NASA Astrophysics Data System (ADS)

Singh, V.; Seehra, M. S.; Manivannan, A.; Kumta, P. N.

2012-04-01

Magnetic properties of Li0.5Mg0.5MnO3-δ nanoparticles (size ≃ 20 nm) synthesized by the Pechini method are investigated using temperature dependence of its magnetization (M) and electron magnetic resonance (EMR) spectra at 9.286 GHz. Analysis of the x-ray diffraction spectra yields its structure to be a cubic defect spinel with the formula 4(Li0.5Mg0.5MnO2.75) = 3{[Li2/3Mg1/3][Mn4/3Mg1/3□1/3]O11/3]} so that Mn occupies the octahedral B-sites only. The data of M versus T yields a blocking temperature TB ≃ 9 K above which the Curie-Weiss law variation with θ = 13 K and μ = 3.96μB characteristic of Mn4+ ions is established. For T < 9 K, temperature dependent coercivity and remanence are observed. The observed temperature dependence of the EMR parameters (linewidth ΔH, resonance field Hr, and intensity Io) for T < 30 K is interpreted in terms of TB (EMR) ≃ 30 K. Formation of ferromagnetic Mn4+ clusters, resulting from the co-presence of non-magnetic Mg2+ and vacancies on the B-sites, is inferred.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries

PubMed Central

McNulty, David; Geaney, Hugh; O’Dwyer, Colm

2017-01-01

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li2O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications. PMID:28186183

Synthesis and electrochemical properties of Li2/3Ni1/3Mn2/3O2 as a novel 5 V class positive electrode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chiba, Kazuki; Shikano, Masahiro; Sakaebe, Hikari

2016-02-01

A lithium nickel manganese oxide, O3-Li2/3Ni1/3Mn2/3O2, is synthesized from the precursor, P3-Na2/3Ni1/3Mn2/3O2, by a Na+/Li+ ion exchange reaction using molten salt. Post-heating at 300, 400, 500, 600, and 700 °C is carried out for 5 h in air. The products are characterized by powder XRD, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), SEM, 6Li-magic-angle-spinning-NMR, and electrochemical measurements. The charge/discharge profiles of O3-Li2/3Ni1/3Mn2/3O2, thermally treated at 500 °C, show a high-potential plateau region at 4.8 V. Furthermore, sloping voltage profiles are observed at an average voltage of 3.21 V. An initial discharge capacity of 257 mA h g-1 is obtained between 2.0 and 4.8 V with a current density of 15 mA g-1 at 25 °C. This capacity corresponds to 0.90 electron transfers per formula unit. This study shows that Post-heating of O3-Li2/3Ni1/3Mn2/3O2 is effective to improve its electrochemical properties.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries.

PubMed

McNulty, David; Geaney, Hugh; O'Dwyer, Colm

2017-02-10

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li 2 O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications.

Unified structure theory of icosahedral quasicrystals: Evidence from neutron powder diffraction patterns that AlCrFeMnSi, AlCuLiMg, and TiNiFeSi icosahedral quasicrystals are twins of cubic crystals containing about 820 or 1012 atoms in a primitive unit cube

PubMed Central

Pauling, Linus

1988-01-01

A unified structure theory of icosahedral quasicrystals, combining the twinned-cubic-crystal theory and the Penrose-tiling-six-dimensional-projection theory, is described. Values of the primitive-cubic lattice constant for several quasicrystals are evaluated from x-ray and neutron diffraction data. The fact that the low-angle diffraction maxima can be indexed with cubic unit cells provides additional support for the twinned-cubic-crystal theory of icosahedral quasicrystals. PMID:16593990

Computational simulation of subatomic-resolution AFM and STM images for graphene/hexagonal boron nitride heterostructures with intercalated defects

NASA Astrophysics Data System (ADS)

Lee, Junsu; Kim, Minjung; Chelikowsky, James R.; Kim, Gunn

2016-07-01

Using ab initio density functional calculations, we predict subatomic-resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) images of vertical heterostructures of graphene/hexagonal boron nitride (h-BN) with an intercalated metal atom (Li, K, Cr, Mn, Co, or Cu), and study the effects of the extrinsic metal defect on the interfacial coupling. We find that the structural deformation of the graphene/h-BN layer caused by the metal defect strongly affects the AFM images, whereas orbital hybridization between the metal defect and the graphene/h-BN layer characterizes the STM images.

Application of microwave digestion to the analysis of peat

USGS Publications Warehouse

Papp, C.S.E.; Fischer, L.B.

1987-01-01

A microwave digestion technique for the dissolution of peat is described and compared with a dry ashing method and a nitric - perchloric - hydrofluoric acid wet digestion. Peat samples with different organic matter contents were used and Ca, Mg, Fe, AI, Na, K, Mn, Zn, Cu and Li were determined by atomic absoprtion spectrometry. The results obtained using the three dissolution techniques were in good agreement. The microwave method has the advantage of digesting the samples in less than 2 h and uses less acid than the conventional wet digestion method. Keeping the volume of the acid mixture as small as possible minimises contamination and leads to lower blank values.

Synthesis, structural, optical and dielectric properties of transition metal doped ZnMnO nanoparticles by sol-gel combustion technique

NASA Astrophysics Data System (ADS)

Dar, M. A.; Varshney, Dinesh

2018-02-01

Nanocrystalline samples of Zn0.94Mn0.06O and transition metal (TM) doped Zn0.94Mn0.01TM0.05O (TM = Co, Ni, and Cu) were prepared by sol-gel auto combustion method. X-ray diffraction (XRD) pattern infers that all synthesized samples except Zn0.94Mn0.01Ni0.05O and Zn0.94Mn0.01Cu0.05O with secondary phases of NiO and CuO are in single phase with hexagonal wurtzite structure (P63mc space group). Raman spectroscopy reveals four vibrational phonon modes are centered at 331, 380, 410, and 438 cm-1, assigned as E2 (H)-E2(L), A1(TO), E1(TO), and E1(LO) modes, respectively. A Raman spectrum of Zn0.94Mn0.01TM0.05O is entirely different from undoped Zn0.94Mn0.06O sample. Also, the infrared spectrum of transition metal doped samples is completely different from undoped Zn0.94Mn0.06O. Similar spectra are observed for Zn0.94Mn0.01Co0.05O, Zn0.94Mn0.01NiO, Zn0.94Mn0.01Cu0.05O and Zn0.94Mn0.01Zn0.05O samples. It was found that the band gap of Zn0.94Mn0.06O increased from 3.19 to 3.25eV by doping 5% transition metal oxide. Improved dielectric constant and reduced dielectric loss is measured for Zn0.94Mn0.01Ni/Cu0.05O as compared to Zn0.94Mn0.06O.

Fabrication and performance of a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O thin film detector

NASA Astrophysics Data System (ADS)

Zhou, Wei; Yin, Yiming; Yao, Niangjuan; Jiang, Lin; Qu, Yue; Wu, Jing; Gao, Y. Q.; Huang, Jingguo; Huang, Zhiming

2018-01-01

A thermal sensitive infrared and THz detector was fabricated by a double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films. The Mn-Co-Ni-O material, as one type of transition metal oxides, has long been used as a candidate for thermal sensors or infrared detectors. The resistivity of a most important Mn-Co-Ni-O thin film, Mn1. 96Co0.96Ni0.48O4(MCN) , is about 200 Ω·cm at room temperature, which ranges about 2 orders larger than that of VOx detectors. Therefore, the thickness of a typical squared Mn-Co-Ni-O IR detector should be about 10 μm, which is too large for focal plane arrays applications. To reduce the resistivity of Mn-Co-Ni-O thin film, 1/6 of Co element was replaced by Cu. Meanwhile, a cover layer of MCN film was deposited onto the Mn-Co-Ni-Cu-O film to improve the long term stability. The detector fabricated by the double layered Mn-Co-Ni-O/Mn-Co-Ni-Cu-O films showed large response to blackbody and 170 GHz radiation. The NEP of the detector was estimated to be the order of 10-8 W/Hz0. 5. By applying thermal isolation structure and additional absorption materials, the detection performance can be largely improved by 1-2 orders according to numerical estimation. The double layered Mn-Co-Ni-O film detector shows great potentials in applications in large scale IR detection arrays, and broad-band imaging.

Gradient Mn-La-Pt Catalysts with Three-layered Structure for Li-O2 battery

PubMed Central

Cai, Kedi; Yang, Rui; Lang, Xiaoshi; Zhang, Qingguo; Wang, Zhenhua; He, Tieshi

2016-01-01

Gradient Mn-La-Pt catalysts with three-layered structure of manganese dioxide (MnO2), lanthanum oxide (La2O3), and Platinum (Pt) for Li-O2 battery are prepared in this study. The mass ratio of the catalysts is respectively 5:2:3, 4:2:4, and 3:2:5 (MnO2: La2O3: Pt) which is start from the side of the electrolyte. The relationship between morphology structure and electrochemical performance of gradient catalyst is investigated by energy dispersive spectrometry and constant current charge/discharge test. The Li-O2 battery based on gradient Mn-La-Pt catalysts shows high discharge specific capacity (2707 mAh g−1), specific energy density (8400 Wh kg−1) and long cycle life (56 cycles). The improvement of the Li-O2 battery discharge capacity is attributed to the gradient distribution of MnO2 and Pt and the involvement of La2O3 that can improve the energy density of the battery. More important, this work will also provide new ideas and methods for the research of other metal-air battery. PMID:27731340

Effect of Composition on the Voltage Fade Phenomenon in Lithium-, Manganese-Rich xLiMnO 3•(1-x)LiNi aMn bCo cO 2: A Combinatorial Synthesis Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vu, Anh; Qin, Yan; Bareno, Javier

2015-10-30

The effect of composition on the voltage fade phenomenon was probed using combinatorial synthesis methods. In compositions that have the general formula, (Li 2MnO 3) a(LiNiO 2) b(LiMnO 2) c(LiCoO 2) d, where 0 ≤ a≤0.83, 0.15 ≤ b ≤ 0.42, 0 ≤ c ≤ 0.85, and 0 ≤ d ≤ 0.30 (a + b + c + d = 1), the dependence of features in the x-ray diffraction pattern and of voltage fade on composition were identified and mapped. The observed values of voltage fade indicated that it displayed some sensitivity to composition, but that the sensitivity was notmore » large. The values of voltage fade were found to be amenable to statistical modeling. The model indicated that it may be possible to lower the value of voltage fade below 0.01% by adjusting the composition of the system; however, the composition is not expected to have the layered–layered structure.« less

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Dziembaj, Roman; Molenda, Marcin

2016-01-01

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material. PMID:28773819

Lithium-Rich Nanoscale Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 Cathode Material Prepared by Co-Precipitation Combined Freeze Drying (CP-FD) for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Ying; Li, Yu; Wu, Chuan

Nanoscale Li-rich Li1.2Mn0.54Ni0.13Co0.13O2 material is synthesized by a co-precipitation combined freeze drying (CP-FD) method, and compared with a conventional co-precipitation method combined vacuum drying (CP-VD). With the combination of X-ray diffraction (XRD) and scanning electron microscopy (SEM), it is found that the sample from CP-FD method consists of a pure phase with good crystallinity and small, homogenous particles (100-300 nm) with uniform particle size distribution. Inductively coupled plasma spectroscopy (ICP) shows that the sample has a stoichiometric ratio of n((Li)): n((Mn)): n((Ni)): n((Co))=9: 4: 1: 1; and its Brunauer-Emmett-Teller (BET) specific surface area is 5.749 m(2)g(-1). This sample achieves excellentmore » electrochemical properties: its initial discharge capacities are 298.9 mAhg(-1) at 0.1C (20 mAg(-1)), 246.1 mAhg(-1) at 0.5C, 215.8 mAhg(-1) at 1C, and 154.2 mAhg(-1) at 5C (5C charge and 5C discharge), as well as good cycling performance. In addition, the Li+ chemical diffusion coefficient of Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by the CP-FD method is 4.59 x 10(-11) cm(2) s(-1), which is higher than that of the Li1.2Mn0.54Ni0.13Co0.13O2 material prepared by CP-VD. This phenomenon illustrates the potential for Li1.2Mn0.54Ni0.13Co0.13O2 with good rate performance synthesized by CP-FD method.« less

Molten salt synthesis and characterization of Li4Ti5-xMnxO12 (x = 0.0, 0.05 and 0.1) as anodes for Li-ion batteries

NASA Astrophysics Data System (ADS)

Nithya, V. D.; Kalai Selvan, R.; Vediappan, Kumaran; Sharmila, S.; Lee, Chang Woo

2012-11-01

Sub-micrometer sized Li4Ti5-xMnxO12 (x = 0.0, 0.05 and 0.1) particles were synthesized by a single step molten salt method using LiCl-KCl as a flux. The synthesized material was structurally characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectra. The XRD analysis revealed the particles to be highly crystalline and have a face-centered cubic spinel structure. The presence of possible functional group was confirmed through FTIR analysis. The FE-SEM images showed the particles to be polyhedral in shape with uniform size distribution. It was also revealed that there was a particle size reduction with the effect of Mn4+ dopant ions. The electrochemical studies performed using cyclic voltammogram (CV), charge-discharge, and electrochemical impedance analysis (EIS) indicate that Li4Ti4.9Mn0.1O4 possesses a better discharge capacity (305 mAh/g), cycling stability, and charge carrier conductivity than both Li4Ti4.95Mn0.05O12 (265 mAh/g) and Li4Ti5O12 (240 mAh/g). The cycling stability reveals that the acceptable capacity fading was observed even after 20th cycle. The results of electrochemical studies infer that Li4Ti4.9Mn0.1O4 could be utilized as a suitable anode material for Li-ion batteries.

Structural and thermal stabilities of layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials in 18650 high power batteries

NASA Astrophysics Data System (ADS)

He, Yan-Bing; Ning, Feng; Yang, Quan-Hong; Song, Quan-Sheng; Li, Baohua; Su, Fangyuan; Du, Hongda; Tang, Zhi-Yuan; Kang, Feiyu

The structural and thermal stabilities of the layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni 1/3Co 1/3Mn 1/3)O 2/graphite high power batteries. The Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode and the Joule heat that results from the great increase in the total resistance (R cell) of batteries. The reactions of fully charged Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.

Molecular dynamics simulations of spinels: LiMn2O4 and Li4Mn5O12 at high temperatures

NASA Astrophysics Data System (ADS)

Ledwaba, R. S.; Matshaba, M. G.; Ngoepe, P. E.

2015-04-01

Energy storage technologies are critical in addressing the global challenge of clean sustainable energy. Spinel lithium manganates have attracted attention due to their electrochemical properties and also as promising cathode materials for lithium-ion batteries. The current study focused on the effects of high temperatures on the materials, in order to understand the sustainability in cases where the battery heats up to high temperature and analysis of lithium diffusion aids in terms of intercalation host compatibility. It is also essential to understand the high temperature behaviour and lithium ion host capability of these materials in order to perform the armorphization and recrystalization of spinel nano-architectures. Molecular dynamics simulations carried out to predict high temperature behaviour of the spinel systems. The NVE ensemble was employed, in the range 300 - 3000K. The melting temperature, lithium-ion diffusion and structural behaviour were monitored in both supercell systems. LiMn2O4 indicated a diffusion rate that increased rapidly above 1500K, just before melting (˜1700K) and reached its maximum diffusion at 2.756 × 10-7 cm2s-1 before it decreased. Li4Mn5O12 indicated an exponential increase above 700K reaching 8.303 × 10-7 cm2s-1 at 2000K and allowing lithium intercalation even above its melting point of around 1300K. This indicated better structural stability of Li4Mn5O12 and capability to host lithium ions at very high temperatures (up to 3000 K) compared to LiMn2O4.

Vascular plants as ecological indicators of metals in alpine vegetation (Karkonosze, SW Poland).

PubMed

Wojtuń, Bronisław; Samecka-Cymerman, Aleksandra; Żołnierz, Ludwik; Rajsz, Adam; Kempers, Alexander J

2017-08-01

Calluna vulgaris, Carex rigida, Deschampsia flexuosa, Nardus stricta and Vaccinium myrtillus are abundant in the vegetation of mountainous areas in Northern and Central Europe. Knowledge of their ability to accumulate increased amounts of metals could be useful in the evaluation of environmental pollution in the alpine tundra of high mountains. Additionally, this investigation may contribute to understanding the rate and direction of recent vegetation change in Karkonosze and similar types of environments. Our investigation revealed that Carex rigida, C. vulgaris and V. myrtillus contain excessive Mn concentrations in shoots with the highest BF for this element compared to the BFs of other elements. C. rigida, with Cu, Mn and Zn concentrations exceeding the toxicity thresholds for plants, seems to be the best metal phytoaccumulator for Nardus stricta grasslands Carici (rigidae)-Nardetum (CrN) and alpine heathlands Carici (rigidae)-Festucetum airoidis (CrFa) associations in the Karkonosze. Based on relevant BFs >1, it can be stated that the following plant available metals were transferred to shoots: Cu, Mn and Ni by C. vulgaris; Cd, Cu, Mn, Ni and Zn by C. rigida; Cd, Cu, Mn, Ni and Zn by D. flexuosa; Cu, Mn, Ni and Zn by N. stricta and Cu, Mn and Zn by V. myrtillus.

First-principles spin-transfer torque in CuMnAs |GaP |CuMnAs junctions

NASA Astrophysics Data System (ADS)

Stamenova, Maria; Mohebbi, Razie; Seyed-Yazdi, Jamileh; Rungger, Ivan; Sanvito, Stefano

2017-02-01

We demonstrate that an all-antiferromagnetic tunnel junction with current perpendicular to the plane geometry can be used as an efficient spintronic device with potential high-frequency operation. By using state-of-the-art density functional theory combined with quantum transport, we show that the Néel vector of the electrodes can be manipulated by spin-transfer torque. This is staggered over the two different magnetic sublattices and can generate dynamics and switching. At the same time the different magnetization states of the junction can be read by standard tunneling magnetoresistance. Calculations are performed for CuMnAs |GaP |CuMnAs junctions with different surface terminations between the antiferromagnetic CuMnAs electrodes and the insulating GaP spacer. We find that the torque remains staggered regardless of the termination, while the magnetoresistance depends on the microscopic details of the interface.

Heavy metals in water, sediments, plants and fish of Kali Nadi U. P. (India)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ajmal, M.; Uddin, R.; Khan, A.U.

1988-01-01

The distribution of heavy metals viz., Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the water, sediments, plants and fish samples collected from the Kali Nadi (India) have been determined. The studies have shown that there was considerable variation in the concentration of heavy metals from one sampling station to the other which may be due to the variation in the quality of industrial and sewage wastes being added to the river at different places. The orders of the concentration of heavy metals in water, sediments, plants (Eicchornia crassipes) and fish (Heteropnuestes fossilis) were Fe > Znmore » > Cu > Mn > Cr > Ni > Pb > Co > Cd; Fe > Zn > Mn > Ni > Cr > Co > Cu > Pb > Cd; Fe > Mn > Zn > Cu > Ni > Co > Pb > Cr > Cd and Fe > Zn > Mn > Ni > Pb >Co > Cr > Cu > Cd, respectively.« less

Dielectric properties and nonlinear I-V electrical behavior of (Li1+, Al3+) co-doped CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Sun, Li; Ni, Qing; Guo, Jianqin; Cao, Ensi; Hao, Wentao; Zhang, Yongjia; Ju, Lin

2018-06-01

(Li1+, Al3+) co-doped CaCu3Ti4O12 ceramics (CaCu3-2 x Li x Al x Ti4O12, x = 0.05, 0.1, 0.15) were prepared by a sol-gel method and were sintered at 1020-1080 °C for 8 h to improve the geometric microstructure, dielectric and nonlinear I-V electrical properties. Notably, very high dielectric constant of 1 × 105 with good dielectric-frequency as well as dielectric-temperature stability can be achieved in CaCu2.8Li0.1Al0.1Ti4O12 ceramic sintered at 1060 °C. The average grain sizes, resistivity and the non-Ohmic properties are also improved compared to pure CaCu3Ti4O12. These results indicate that (Li1+, Al3+) co-doping at the Cu2+ site can improve the dielectric properties of CaCu3Ti4O12, supporting the internal barrier layer capacitance effect of Schottky barriers at grain boundaries.

Coating magnetic CuFe2O4 nanoparticles with OMS-2 for enhanced degradation of organic pollutants via peroxymonosulfate activation

NASA Astrophysics Data System (ADS)

Ye, Peng; Wu, Deming; Wang, Manye; Wei, Yi; Xu, Aihua; Li, Xiaoxia

2018-01-01

A heterogeneous magnetic CuFe2O4@OMS-2 catalyst was fabricated through a facile solvent-free process using Mn(CH3COO)2 and KMnO4 in the presence of CuFe2O4. It was found that the BET surface area of OMS-2 as well as the ratio of low-valent manganese species significantly increased in the hybrid catalyst, due to interactions between CuFe2O4 and the precursor of amorphous manganese oxide. Acid Orange 7 (AO7) and other organic pollutants could be completely degraded by the CuFe2O4@OMS-2 catalyst within 30 min in the presence of peroxymonosulfate (PMS), while CuFe2O4 and OMS-2 showed no significant activity for the reaction. The hybrid catalyst also exhibited excellent long-term stability and could be easily recovered with the assistance of an external magnetic field. A possible degradation mechanism for the synergistic effects of different valent metal species and reactive radicals was proposed, which involved the electron transfer from Mn(III) or Mn(II) species to PMS with the generation of sulfate and hydroxyl radicals, and from AO7 and Cu(I) in CuFe2O4 to Mn(IV) and Mn(III) to reduce these Mn species.

Bioaccumulation of Zn, Cu and Mn in the caviar and muscle of Persian sturgeon (Acipenser persicus) from the Caspian Sea, Iran.

PubMed

Mashroofeh, Abdulreza; Bakhtiari, Alireza Riyahi; Pourkazemi, Mohammad

2012-12-01

Concentrations of Zn, Cu and Mn were examined in caviar and muscle of the Persian sturgeon (Acipenser persicus) collected from coastal waters of south Caspian Sea during March and April, 2011. Mean Zn, Cu and Mn concentrations in caviar samples were 21.48, 2.05 and 1.66 μg g(-1) wet weight basis, respectively. The mean Zn, Cu and Mn concentrations in muscle tissues were 7.49, 1.00 and 0.34 μg g(-1) wet weight basis, respectively. The mean concentrations of Zn and Cu in caviar and muscle samples were under the permissible limits proposed by the United Kingdom's Ministry of Agriculture, Fisheries and Food (2000).

Assessment of total soil and plant trace elements in rice-based production systems in NE Italy

NASA Astrophysics Data System (ADS)

Bini, Claudio; Nadimi-Goki, Mandana; Kato, Yoichi; Vianello, Gilmo; Vittori, Livia; Wahsha, Mohammad; Spiandorello, Massimo

2014-05-01

Macro- and micronutrients concentrations, and PTEs contents in soils and plants (rice) from the rice district in the Venetian territory (NE Italy) have been determined by ICP-MS spectrometry, with the following aims: - to determine the background levels of macro- and microelements in the study area; - to assess possible contamination of soils and plants; - to calculate the Translocation Factor (TF) of metals from soil to plant, and the possible hazard for human health. Four rice plots with different rotation systems were investigated from seedling time to harvesting; sampling of soils (0-30cm) and plants was carried out 4 times during growing season (three replicates). Rice plants were separated into roots, stems, leaves and grains, and then oven-dried. Chemical and physical analyses were carried out at the Soil Science Lab of the University of Bologna and Venice, respectively. The results obtained point to a land with moderate soil contamination by trace elements (namely Li, Sn, Tl, Sr, Ti, Fe). Heavy metal (Sb, As, Be, Cd, Co, Cr, Ni, Pb, Cu, V, Zn ) concentrations in soils are below the threshold indicated by the Italian legislation (DM 152/2006). Cd, Sn, and Ti contents in soils are positively correlated with soil pH, while As, Fe, Li, Ti, Tl and Zn are negatively correlated with organic matter content. With the exception of Strontium, soil metal contents are always correlated between variable couples. HMs in plants vary according to the sampling season, texture and moisture, and soil pH. Most non-essential trace elements are accumulated in rice roots and, only in cases of essential micronutrients, in leaves. Therefore, rice can be assumed as an accumulator plant of As, Pb, Cr, Ba, and Ti, whereas it is as an indicator plant for Cu, Fe, Ni, Mn and Zn. The results of multiple linear regression analysis showed that soil pH has a larger effect on Ba, Cr, Cu, Fe, Mn, Ni, Ti and Zn concentrations in grain than other soil parameters. The average translocation of metals from soil to root was found to be >1, irrespective of the essential/not essential function; conversely, only essential elements ((Cu, Fe, Mn, Zn) are translocated rather easily from roots to leaves (TF ≤1) via phloem (TF< <1), and very little translocated to grains (TF< <1). Therefore, it is suggested that rice could be useful in contaminated-sites restoration projects by the phytostabilization technique. Moreover, there is very limited hazard for human population consuming rice crops. Key Words: Macro- and micronutrients concentrations, heavy metals, trace elements, rice plant, Italy, accumulator plant, indicator plant * Corresponding author. Tel.: +39 3891356251 E-mail address: mandy.nadimi@gmail.com

Influence of Li Addition to Zn-Al Alloys on Cu Substrate During Spreading Test and After Aging Treatment

NASA Astrophysics Data System (ADS)

Gancarz, Tomasz; Pstrus, Janusz; Cempura, Grzegorz; Berent, Katarzyna

2016-12-01

The spreading of Zn-Al eutectic-based alloys with 0.05 wt.%, 0.1 wt.%, and 0.2 wt.% Li on Cu substrate has been studied using the sessile drop method in presence of QJ201 flux. Wetting tests were performed after 1 min, 3 min, 8 min, 15 min, 30 min, and 60 min of contact at temperatures of 475°C, 500°C, 525°C, and 550°C. Samples after spreading at 500°C for 1 min were subjected to aging for 1 day, 10 days, and 30 days at temperature of 120°C, 170°C, and 250°C. The spreadability of eutectic Zn-5.3Al alloy with different Li contents on Cu substrate was determined in accordance with ISO 9455-10:2013-03. Selected solidified solder-substrate couples were, after spreading and aging tests, cross-sectioned and subjected to scanning electron microscopy, energy-dispersive spectroscopy (EDS), and x-ray diffraction (XRD) analysis of the interfacial microstructure. An experiment was designed to demonstrate the effect of Li addition on the kinetics of the formation and growth of CuZn, Cu5Zn8, and CuZn4 intermetallic compound (IMC) phases, during spreading and aging. The IMC layers formed at the interface were identified using XRD and EDS analyses. Increasing addition of Li to Zn-Al alloy caused a reduction in the thickness of the IMC layer at the interface during spreading, and an increase during aging. The activation energy was calculated, being found to increase for the Cu5Zn8 phase but decrease for the CuZn and CuZn4 phases with increasing Li content in the Zn-Al-Li alloys. The highest value of 142 kJ mol-1 was obtained for Zn-Al with 1.0 Li during spreading and 69.2 kJ mol-1 for Zn-Al with 0.05 Li during aging. Aging at 250°C caused an increase in only the Cu5Zn8 layer, which has the lowest Gibbs energy in the Cu-Zn system. This result is connected to the high diffusion of Cu from the substrate to the solder.

CO₂ and O₂ evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study.

PubMed

Wang, Hongsen; Rus, Eric; Sakuraba, Takahito; Kikuchi, Jun; Kiya, Yasuyuki; Abruña, Héctor D

2014-07-01

A three-electrode differential electrochemical mass spectrometry (DEMS) cell has been developed to study the oxidative decomposition of electrolytes at high voltage cathode materials of Li-ion batteries. In this DEMS cell, the working electrode used was the same as the cathode electrode in real Li-ion batteries, i.e., a lithium metal oxide deposited on a porous aluminum foil current collector. A charged LiCoO2 or LiMn2O4 was used as the reference electrode, because of their insensitivity to air, when compared to lithium. A lithium sheet was used as the counter electrode. This DEMS cell closely approaches real Li-ion battery conditions, and thus the results obtained can be readily correlated with reactions occurring in real Li-ion batteries. Using DEMS, the oxidative stability of three electrolytes (1 M LiPF6 in EC/DEC, EC/DMC, and PC) at three cathode materials including LiCoO2, LiMn2O4, and LiNi(0.5)Mn(1.5)O4 were studied. We found that 1 M LiPF6 + EC/DMC electrolyte is quite stable up to 5.0 V, when LiNi(0.5)Mn(1.5)O4 is used as the cathode material. The EC/DMC solvent mixture was found to be the most stable for the three cathode materials, while EC/DEC was the least stable. The oxidative decomposition of the EC/DEC mixture solvent could be readily observed under operating conditions in our cell even at potentials as low as 4.4 V in 1 M LiPF6 + EC/DEC electrolyte on a LiCoO2 cathode, as indicated by CO2 and O2 evolution. The features of this DEMS cell to unveil solvent and electrolyte decomposition pathways are also described.

Behavior of LiFe1-yMnyPO4/C cathode materials upon electrochemical lithium intercalation/deintercalation

NASA Astrophysics Data System (ADS)

Novikova, Svetlana; Yaroslavtsev, Sergey; Rusakov, Vyacheslav; Chekannikov, Andrey; Kulova, Tatiana; Skundin, Alexander; Yaroslavtsev, Andrey

2015-12-01

LiFe1-yMnyPO4/C (y = 0-0.3) nanocomposites are prepared by the sol-gel method, and their properties are characterized with the use of the XRD analysis, SEM, impedance spectroscopy, charge/discharge tests, and Mössbauer spectroscopy. The samples with a low manganese content, LiFe1-yMnyPO4 (y = 0.1, 0.2) are characterized by an increased conductivity. In LiFe1-yMnyPO4 (x = 0.1-0.3), electrochemical lithium deintercalation/intercalation proceeds in two stages which due to the subsequent oxidation/reduction of iron and manganese ions. The LiFe1-yMnyPO4/С (y = 0.1, 0.2) samples show enhanced charge/discharge capacity, especially, at high current density (for LiFe0.9Mn0.1PO4/C, the discharge capacity is equal to 142 and 55 mAh g-1 at a current density of 20 and 1600 mA g-1, respectively). Mn2+ ↔ Mn3+ transition in LiFe1-yMnyPO4 proceeds via the solid solutions formation under gradual changes in the potential. For LiFe0.7Mn0.3PO4, oxidation and reduction of iron ions follow the same scenario. According to the Mössbauer spectroscopy data, manganese is orderly distributed in LixFeIII1-yMnyPO4: iron contains not more than one manganese cation in its nearest neighborhood. Moreover, combination of the Mössbauer spectroscopy and X-ray analysis data indicates that, in the interval where solid solutions exist in LixFe0.7Mn0.3PO4, the regions with an inhomogeneous distribution of divalent and trivalent manganese ions are formed.

Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

2018-05-01

Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

X-ray diffraction analysis of LiCu{sub 2}O{sub 2} crystals with additives of silver atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirotinkin, V. P., E-mail: irotinkin.vladimir@mail.ru; Bush, A. A.; Kamentsev, K. E.

2015-09-15

Silver-containing LiCu{sub 2}O{sub 2} crystals up to 4 × 8 × 8 mm in size were grown by the crystallization of 80(1-x)CuO · 20{sub x}AgNO{sub 3} · 20Li{sub 2}CO{sub 3} (0 ≤ x ≤ 0.5) mixture melt. According to the X-ray spectral and Rietveld X-ray diffraction data, the maximum amount of silver incorporated in the LiCu{sub 2}O{sub 2} structure is about 4 at % relative to the copper content. It was established that silver atoms occupy statistically crystallographic positions of lithium atoms. The incorporation of silver atoms is accompanied by a noticeable increase in parameter c of the LiCu{sub 2}O{submore » 2} rhombic unit cell, a slight increase in parameter a, and a slight decrease in parameter b.« less

Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

DOE PAGES

Xu, Jing; Renfrew, Sara; Marcus, Matthew A.; ...

2017-05-11

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, andmore » charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.« less

Ionomic profiling of Nicotiana langsdorffii wild-type and mutant genotypes exposed to abiotic stresses.

PubMed

Ardini, Francisco; Soggia, Francesco; Abelmoschi, Maria Luisa; Magi, Emanuele; Grotti, Marco

2013-01-01

To provide a new insight into the response of plants to abiotic stresses, the ionomic profiles of Nicotiana langsdorffii specimens have been determined before and after exposure to toxic metals (chromium) or drought conditions. The plants were genetically transformed with the rat glucocorticoid receptor (GR) or the gene for Agrobacterium rhizogenes rolC, because these modifications are known to produce an imbalance in phytohormone equilibria and a significant change in the defence response of the plant. Elemental profiles were obtained by developing and applying analytical procedures based on inductively coupled plasma atomic emission and mass spectrometry (ICP-AES/MS). In particular, the removal of isobaric interferences affecting the determination of Cr and V by ICP-MS was accomplished by use of a dynamic reaction cell, after optimization of the relevant conditions. The combined use of ICP atomic emission and mass spectrometry enabled the determination of 29 major and trace elements (Ba, Bi, Ca, Cd, Co, Cr, Cu, Eu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, P, Pb, Pt, Rb, S, Sb, Sn, Sr, Te, V, W, Y, and Zn) in different parts of the plants (roots, stems, and leaves), with high accuracy and precision. Multivariate data processing and study of element distribution patterns provided new information about the ionomic response of the target organism to chemical treatment or water stress. Genetic modification mainly affected the distribution of Bi, Cr, Mo, Na, and S, indicating that these elements were involved in biochemical processes controlled by the GR or rolC genes. Chemical stress strongly affected accumulation of several elements (Ba, Ca, Fe, Ga, K, Li, Mn, Mo, Na, P, Pb, Rb, S, Sn, Te, V, and Zn) in different ways; for Ca, Fe, K, Mn, Na, and P the effect was quite similar to that observed in other studies after treatment with other transition elements, for example Cu and Cd. The effect of water deficit was less evident, mainly consisting in a decrease of Ba, Cr, Na, and Sr in roots.

Spatial and temporal distribution of metals in suspended particulate matter of the Kali estuary, India

NASA Astrophysics Data System (ADS)

Suja, S.; Kessarkar, Pratima M.; Fernandes, Lina L.; Kurian, Siby; Tomer, Arti

2017-09-01

Major (Al, Fe, Mn, Ti, Mg) and trace (Cu, Zn, Pb, Cr, Ni, Co, Zr, Rb, Sr, Ba, Li, Be, Sc, V, Ga, Nb, Mo, Sn, Sb, Cs, Hf, Ta, Bi, Th, U) elements and particulate organic carbon (POC) concentrations in surface suspended particulate matter (SPM) of the Kali estuary, (central west coast of India) were studied during the pre-monsoon, monsoon and post monsoon seasons to infer estuarine processes, source of SPM and Geoaccumulation Index (Igeo) assigned pollutionIgeo levels. Distribution of SPM indicates the presence of the estuarine turbidity maximum (ETM) during all three seasons near the river mouth and a second ETM during the post monsoon time in the upstream associated with salinities gradient. The SPM during the monsoon is finer grained (avg. 53 μm), characterized by uniformly low normalized elemental concentration, whereas the post and pre monsoon are characterized by high normalized elemental concentration with coarser grain size (avg. 202 μm and 173 μm respectively) with highest ratios in the upstream estuary. The elemental composition and principal component analysis for the upstream estuary SPM support more contribution from the upstream catchment area rocks during the monsoon season; there is additional contribution from the downstream catchment area during the pre and post monsoon period due to the tidal effect. The Kali estuarine SPM has higher Al, Fe, Mn, Ti, Mg, Ni, Co, Ba, Li and V with respect to Average World River SPM (WRSPM). Igeo values for the SPM indicate Kali Estuary to be severely enriched with Mn and moderately enriched with Cu, Zn, Ni, Co, U and Mo in the upstream estuary during pre and post monsoon seasons. Seasonal changes in salinity gradient (reduced freshwater flow due to closing of the dam gates), reduced velocity at meandering region of the estuary and POC of 1.6-2.3% resulted in co-precipitation of trace elements that were further fortified by flocculation and coagulation throughout the water column resulting in metal trapping in the upstream region.

Trace and Ultra-trace Elements in the Deepest Part of the Vostok Ice Core, Antarctica: Geochemical Characterization of the Sub-glacial Lake Environment

NASA Astrophysics Data System (ADS)

Turetta, C.; Planchon, F.; Gabrielli, P.; Cozzi, G.; Cairns, W.; Barbaro, E.; Petit, J. R.; Bulat, S.; Boutron, C.; Barbante, C.

2016-12-01

We present in this study comprehensive data on the occurrence of 25 trace and ultra-trace elements in the deepest part of the Vostok ice core. The determination of Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba, Pb, Bi and U has been performed in the different types of ice encountered from 3271 m to 3609 m of depth, corresponding to atmospheric ice, glacial flour and to accreted ice originating from the freezing of Lake Vostok waters. From atmospheric ice and glacial flour, the relative contributions of primary aerosols were evaluated for each element using a chemical mass balance approach in order to provide a first order evaluation of their partition between soluble (sea-salt) and insoluble (wind-blown dust) fractions in the ice. Sea-salt spray aerosols are the main source of impurities to the ice for certain elements (Na, Mg and K levels, and in a lesser extent to Ca, Sr, Rb, Li and U) while for other elements (Al, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, Sb, Ba and Pb as well as the non sea salt fractions of Mg, K, Ca, Sr, Rb, Li and U) dust inputs appear to primarily control their depositional variability. For the glacial flour, the comparable levels of elements with the overlying atmospheric ice suggest that incorporation of abrasion debris at the glacier is quite limited in the sections considered. For the accreted ice originating from the subglacial waters of Lake Vostok, we observed a major chemical shift in the composition of the ice showing two distinct trends that we assumed to be derived from the chemical speciation of elements. The study of the glacier ice and the glacial flour has allowed us to perform a detailed characterisation of elemental abundances related to the aerosol sources variability and also to illustrate the interaction between the ice-sheet and the bedrock.

Digestibility and retention of zinc, copper, manganese, iron, calcium, and phosphorus in pigs fed diets containing inorganic or organic minerals.

PubMed

Liu, Y; Ma, Y L; Zhao, J M; Vazquez-Añón, M; Stein, H H

2014-08-01

The objective of this experiment was to measure the apparent total tract digestibility (ATTD) and the retention rate of Zn, Cu, Mn, and Fe in pigs fed either inorganic or organic sources of Zn, Cu, Mn, and Fe. The experimental design was a randomized complete block design with a 2 × 3 factorial arrangement of treatments. There were 2 types of diets (corn grits-based or corn-soybean meal [SBM]-based diets) and 3 micromineral treatments (basal micromineral premix [BMM], inorganic micromineral premix [IMM], and organic micromineral premix [OMM]). The BMM contained no added Zn, Cu, Mn, or Fe; the IMM microminerals were provided as sulfates of Zn, Cu, Mn, and Fe at 40, 50, 20, and 100 mg/kg, respectively. The OMM contained the same levels of the 4 microminerals as IMM, but Zn, Cu, Mn, and Fe in this premix were provided by Zn(2-hydroxy-4-methylthio butanoic acid [HMTBa])2, Cu(HMTBa)2, Mn(HMTBa)2, and FeGly, respectively. Forty-eight barrows (initial BW: 31.1 ± 4.2 kg) were housed individually and allowed ad libitum access to the corn grits diet with BMM for 2 wk. All pigs were then moved to metabolism cages and randomly assigned to 1 of the 6 treatment diets with 8 replicates per diet. Fecal and urine samples were collected for 5 d following a 5-d adaptation period. Compared with corn grits diets, pigs fed corn-SBM diets had greater (P < 0.05) absorption and retention of Zn, Cu, and Mn but less (P < 0.05) ATTD of Zn and Cu. Compared with BMM, supplementation of IMM or OMM increased (P < 0.05) absorption, retention, ATTD, and retention rate of Zn, Cu, Mn, and Fe. Compared with IMM, adding OMM to the corn-SBM diet improved (P < 0.05) the absorption and retention of Cu and Mn and the ATTD of Cu, but these differences were not observed in the corn grits diets (interaction, P < 0.05). In addition, adding OMM to the corn-SBM diet increased (P < 0.05) absorption and retention of Zn and Fe and ATTD of Zn, Mn, and Fe compared with adding IMM to the corn-SBM diet. Supplementation of OMM also increased (P < 0.05) the ATTD and retention rate of P in corn-SBM diets. Results indicate that Zn(HMTBa)2 has greater digestibility and Cu(HMTBa)2 and Mn(HMTBa)2 have greater digestibility and retention rates compared with their inorganic sulfates, if included in a corn-SBM diet. Supplementation of organic microminerals also improves the digestibility of P in a corn-SBM diet.

Magnetic properties of Ni-Cu-Mn ferrite system

NASA Astrophysics Data System (ADS)

Roumaih, Kh.

2011-10-01

Three groups according to the substitution of Cu 2+ and Mn 3+ in the system Ni 1-xCu xFe 2-yMn yO 4 ferrite with x = 0.2, 0.5, 0.8, and y varying from 0.0 to 1.0 in steps of 0.25 are prepared by solid state reactions. The phases of the Ni 1-xCu xFe 2-yMn yO 4 ferrite have been confirmed by X-ray diffraction (XRD). The results demonstrate that all of the synthesized materials are spinel with cubic unit cell and the lattice constant increased with increases of the Cu and Mn ions for all samples. The hyperfine interaction was studied by the Mössbauer spectroscopy at room temperature for all samples. The spectra of all samples show two well-resolved Zeeman patterns corresponding to A- and B-sites. The hyperfine field decreases with increasing Cu and Mn ions concentration. The Curie temperature, TC, was calculated from the temperature dependence of magnetization curves. The hysteresis curve recorded at room temperature shows that the samples are ferrimagnetic materials. The cation distribution was estimated from the results of Mössbauer spectroscopy and magnetic measurements.

Biomonitoring of 33 Elements in Blood and Urine Samples from Coastal Populations in Sanmen County of Zhejiang Province.

PubMed

Zhang, Su-jing; Luo, Ru-xin; Ma, Dong; Zhuo, Xian-yi

2016-04-01

To determine the normal reference values of 33 elements, Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, Hg, Li, Mg, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sr, Th, Ti, Tl, U, V, Zn and Zr, in the blood and urine samples from the general population in Sanmen County of Zhejiang province, a typical coastal area of eastern China. The 33 elements in 272 blood and 300 urine samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The normality test of data was conducted using SPSS 17.0 Statistics. The data was compared with other reports. The normal reference values of the 33 elements in the blood and urine samples from the general population in Sanmen County were obtained, which of some elements were found to be similar with other reports, such as Co, Cu, Mn and Sr, while As, Cd, Hg and Pb were generally found to be higher than those previously reported. There was a wide variation between the reports from different countries in blood Ba. The normal reference values of the 33 elements in the blood and urine samples from the general population in Sanmen County are established, and successfully applied to two poisoning cases.

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rong, Xiaohui; Liu, Jue; Hu, Enyuan

Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. In this paper, a P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Finally, different from Li 2RuO 3 or Li 2IrO 3 with strong metal-oxygen (M-O) bonding, for P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with relatively weak Mn-O covalentmore » bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O 2 gas.« less

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

DOE PAGES

Rong, Xiaohui; Liu, Jue; Hu, Enyuan; ...

2017-11-01

Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. In this paper, a P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Finally, different from Li 2RuO 3 or Li 2IrO 3 with strong metal-oxygen (M-O) bonding, for P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with relatively weak Mn-O covalentmore » bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O 2 gas.« less

RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Yue-Feng; Chen, Yuan; Xu, Gui-Liang

RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presentedmore » much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge process of Li-O-2 battery.« less

Electrodeposition and Characterization of Mn-Cu-Zn Alloys for Corrosion Protection Coating

NASA Astrophysics Data System (ADS)

Tsurtsumia, Gigla; Gogoli, David; Koiava, Nana; Kakhniashvili, Izolda; Jokhadze, Nunu; Lezhava, Tinatin; Nioradze, Nikoloz; Tatishvili, Dimitri

2017-12-01

Mn-Cu-Zn alloys were electrodeposited from sulphate bath, containing citrate or EDTA and their mixtures as complexing ligands. The influence of bath composition and deposition parameters on alloys composition, cathodic current efficiency and structural and electrochemical properties were studied. At a higher current density (≥ 37.5 A dm-2) a uniform surface deposit of Mn-Cu-Zn was obtained. Optimal pH of electrolyte (0.3 mol/dm3Mn2+ + 0.6 mol/dm3 (NH4)2SO4 +0.1 mol/dm3Zn2++0.005 mol/dm3 Cu2++ 0.05mol/dm3Na3Cit + 0.15mol/dm3 EDTA; t=300C; τ=20 min) for silvery, nonporous coating of Mn-Cu-Zn alloy was within 6.5-7.5; coating composition: 71-83% Mn, 6-7.8% Cu, 11.5-20% Zn, current efficiency up to 40%. XRD patterns revealed BCT (body centred tetragonal) γ-Mn solid phase solution (lattice constants a=2.68 Å c=3.59 Å). Corrosion measurements of deposited alloys were performed in aerated 3.5% NaCl solution. The corrosion current density (icorr) of the electrodeposited alloys on carbon steel was 10 times lower than corrosion rate of pure zinc and manganese coatings. Triple alloy coatings corrosion potential (Ecorr = -1140 mV vs. Ag/AgCl) preserved negative potential value longer (more than three months) compared to carbon steel substrate (Ecorr = -670 mV vs. Ag/AgCl). Tafel polarization curves taken on Mn-Cu-Zn alloy coating in aerated 3.5% NaCl solution did not show a typical passivation behaviour which can be explained by formation oflow solubility of adherent corrosion products on the alloy surface. Corrosion test of Mn-Cu-Zn electrocoating in chlorine environment shows that it is the best cathodic protective coating for a steel product.

Structure–property insights into nanostructured electrodes for Li-ion batteries from local structural and diffusional probes

DOE PAGES

Laveda, Josefa Vidal; Johnston, Beth; Paterson, Gary W.; ...

2017-12-04

Microwave heating presents a faster, lower energy synthetic methodology for the realization of functional materials. Here, we demonstrate for the first time that employing this method also leads to a decrease in the occurrence of defects in olivine structured LiFe 1–xMn xPO 4. For example, the presence of antisite defects in this structure precludes Li + diffusion along the b-axis leading to a significant decrease in reversible capacities. Total scattering measurements, in combination with Li + diffusion studies using muon spin relaxation (μ+SR) spectroscopy, reveal that this synthetic method generates fewer defects in the nanostructures compared to traditional solvothermal routes.more » Our interest in developing these routes to mixed-metal phosphate LiFe 1–xMn xPO 4 olivines is due to the higher Mn 2+/ 3+ redox potential in comparison to the Fe 2+/ 3+ pair. Here, single-phase LiFe 1–xMn xPO 4 (x = 0, 0.25, 0.5, 0.75 and 1) olivines have been prepared following a microwave-assisted approach which allows for up to 4 times faster reaction times compared to traditional solvothermal methods. Interestingly, the resulting particle morphology is dependent on the Mn content. We also examine their electrochemical performance as active electrodes in Li-ion batteries. In conclusion, these results present microwave routes as highly attractive for reproducible, gram-scale syntheses of high quality nanostructured electrodes which display close to theoretical capacity for the full iron phase.« less

Structure–property insights into nanostructured electrodes for Li-ion batteries from local structural and diffusional probes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laveda, Josefa Vidal; Johnston, Beth; Paterson, Gary W.

Microwave heating presents a faster, lower energy synthetic methodology for the realization of functional materials. Here, we demonstrate for the first time that employing this method also leads to a decrease in the occurrence of defects in olivine structured LiFe 1–xMn xPO 4. For example, the presence of antisite defects in this structure precludes Li + diffusion along the b-axis leading to a significant decrease in reversible capacities. Total scattering measurements, in combination with Li + diffusion studies using muon spin relaxation (μ+SR) spectroscopy, reveal that this synthetic method generates fewer defects in the nanostructures compared to traditional solvothermal routes.more » Our interest in developing these routes to mixed-metal phosphate LiFe 1–xMn xPO 4 olivines is due to the higher Mn 2+/ 3+ redox potential in comparison to the Fe 2+/ 3+ pair. Here, single-phase LiFe 1–xMn xPO 4 (x = 0, 0.25, 0.5, 0.75 and 1) olivines have been prepared following a microwave-assisted approach which allows for up to 4 times faster reaction times compared to traditional solvothermal methods. Interestingly, the resulting particle morphology is dependent on the Mn content. We also examine their electrochemical performance as active electrodes in Li-ion batteries. In conclusion, these results present microwave routes as highly attractive for reproducible, gram-scale syntheses of high quality nanostructured electrodes which display close to theoretical capacity for the full iron phase.« less

Pulsed sonication for alumina coatings on high-capacity oxides: Performance in lithium-ion cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pol, Vilas G.; Li, Yan; Dogan, Fulya

2014-07-01

High-capacity xLi2MnO3•(1-x)LiMO2 (M=Ni, Mn, Co) oxides show relatively rapid performance degradation when cycled at voltages >4.5V vs. Li/Li+. Previous research has indicated that modifying the oxide surfaces with coatings, such as alumina, reduces cell impedance rise and improves capacity retention. In this article, we demonstrate pulsed-sonication as a rapid and effective approach for coating alumina on Li1.2Ni0.175Mn0.525Co0.1O2 (0.5Li2MnO3•0.5LiNi0.44Mn0.31Co0.25O2) particles. Oxide integrity and morphology is maintained after the sonochemical process and subsequent heat-treatment. Energy dispersive spectroscopy (EDS) X-ray elemental maps show uniform coating of all secondary particles. 27Al Magic Angle Spinning (MAS) NMR data confirm the presence of alumina and mainlymore » indicate octahedral aluminum occupancy in a six-coordinate environment with oxygen. Full cells containing electrodes with the alumina-coated particles demonstrate lower initial impedance rise and better capacity retention during extended cycling to high voltages. However, the coating has a negligible effect on the voltage hysteresis and voltage fade behavior displayed by these oxides. The various data indicate that the pulsed sonochemical technique is a viable approach for coating oxide particles. The methodology described herein can easily be extended beyond alumina to include coatings such as AlF3, MgO, and MgF2.« less

Cerium and zinc: Dual-doped LiMn 2O 4 spinels as cathode material for use in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Rajalakshmi, R.

Pristine spinel lithium manganese oxide (LiMn 2O 4) and zinc- and cerium-doped lithium manganese oxide [LiZn xCe yMn 2- x- yO 4 (x = 0.01-0.10; y = 0.10-0.01)] are synthesized for the first time via the sol-gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol-gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge-discharge studies of LiMn 2O 4 samples heated at 850 °C exhibit a discharge capacity of 122 mAh g -1 and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn 0.01Ce 0.01Mn 1.98O 4 is found to be superior (124 mAh g -1), with a low capacity fade (0.1 mAh g -1 cycle -1) over the investigated 10 cycles.

Preparation of LiMn{sub 2}O{sub 4} cathode thin films for thin film lithium secondary batteries by a mist CVD process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tadanaga, Kiyoharu, E-mail: tadanaga@chem.osakafu-u.ac.jp; Yamaguchi, Akihiro; Sakuda, Atsushi

2014-05-01

Highlights: • LiMn{sub 2}O{sub 4} thin films were prepared by using the mist CVD process. • An aqueous solution of lithium and manganese acetates is used for the precursor solution. • The cell with the LiMn{sub 2}O{sub 4} thin films exhibited a capacity of about 80 mAh/g. • The cell showed good cycling performance during 10 cycles. - Abstract: LiMn{sub 2}O{sub 4} cathode thin films for thin film lithium secondary batteries were prepared by using so-called the “mist CVD process”, employing an aqueous solution of lithium acetate and manganese acetate, as the source of Li and Mn, respectively. The aqueousmore » solution of starting materials was ultrasonically atomized to form mist particles, and mists were transferred by nitrogen gas to silica glass substrate to form thin films. FE-SEM observation revealed that thin films obtained by this process were dense and smooth, and thin films with a thickness of about 750 nm were obtained. The electrochemical cell with the thin films obtained by sintering at 700 °C exhibited a capacity of about 80 mAh/g, and the cell showed good cycling performance during 10 cycles.« less

Physical and photoelectrochemical properties of the spinel LiMn2O4 and its application in photocatalysis

NASA Astrophysics Data System (ADS)

Douafer, S.; Lahmar, H.; Benamira, M.; Rekhila, G.; Trari, M.

2018-07-01

Nanocrystalline lithium manganese oxide (LiMn2O4), synthesized by the sol-gel method, crystallizes in the spinel structure. The physical, electrical, and photoelectrochemical properties were studied for the photocatalytic degradation of methyl orange, a toxic compound, under solar irradiation. The diffuse reflectance spectrum allowed the direct band gap (1.99 eV) to be calculated. The Fourier transform IR spectrum contained all the characteristic peaks of the spinel LiMn2O4, which exhibited n-type behavior. The thermal evolution of the electrical conductivity exhibited an Arrhenius-type behavior with an activation energy of 0.27 eV. The Mott-Schottky curve allowed the determination of the flat band potential (-0.24 V vs. the saturated calomel electrode) as well as the carrier density (1.78 × 1021 cm-3). The detoxification of water containing methyl orange with LiMn2O4 as a photocatalyst was successfully completed. Total degradation for an initial concentration of 10-4 M methyl orange at pH ∼3 and 25 °C was obtained in less than 5 h under solar irradiation. No adsorption was obtained in the dark in the presence of LiMn2O4.

Synthesis and electrochemical characterization of LiMn0.6Fe0.4PO4/C cathode material via a modified-solid state reaction method.

PubMed

Kim, Hyun-Ju; Jin, Bong-Soo; Bae, Dong-Sik; Kim, Seong-Bae; Kim, Hyun-Soo

2013-05-01

LiMn0.6Fe0.4PO4/C cathode material is synthesized via a modified-solid state reaction method. The calcination temperature is adjusted in the range of 500-700 degrees C for 10 h. The crystal structure, morphology, and carbon coating layer of the synthesized LiMn0.6Fe0.4PO4/C are analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The electrochemical performance of LiMn0.6Fe0.4PO4/C, such as initial capacity, rate capability, cycling performance and EIS is also evaluated. The synthesized cathode material shows around 100-200 nm of primary particle size with no impurities. The highest initial discharge capacity of 162.1 mA h g(-1) and columbic efficiency of 98.5% are obtained at a heat treatment temperature of 600 degrees C. In addition, LiMn0.6Fe0.4PO4/C active material shows the high capacity retention of 85% at 5 C compared to 0.2 C. It also shows the excellent capacity retention of 97.5% after the 50th charge/discharge.

Hydrogen determination in chemically delithiated lithium ion battery cathodes by prompt gamma activation analysis

NASA Astrophysics Data System (ADS)

Alvarez, Emilio, II

2007-12-01

Lithium ion batteries, due to their relatively high energy density, are now widely used as the power source for portable electronics. Commercial lithium ion cells currently employ layered LiCoO2 as a cathode but only 50% of its theoretical capacity can be utilized. The factors that cause the limitation are not fully established in the literature. With this perspective, prompt gamma-ray activation analysis (PGAA) has been employed to determine the hydrogen content in various oxide cathodes that have undergone chemical extraction of lithium (delithiation). The PGAA data is complemented by data obtained from atomic absorption spectroscopy (AAS), redox titration, thermogravimetric analysis (TGA), and mass spectroscopy to better understand the capacity limitations and failure mechanisms of lithium ion battery cathodes. As part of this work, the PGAA facility has been redesigned and reconstructed. The neutron and gamma-ray backgrounds have been reduced by more than an order of magnitude. Detection limits for elements have also been improved. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. The data indicates that while delithiated layered Li1- xCoO2, Li1-xNi 1/3Mn1/3Co1/3O2, and Li1- xNi0.5Mn0.5O2 take significant amounts of hydrogen into the lattice during deep extraction, orthorhombic Li 1-xMnO2, spinel Li1- xMn2O4, and olivine Li1- xFePO4 do not. Layered LiCoO2, LiNi 0.5Mn0.5O2, and LiNi1/3Mn1/3Co 1/3O2 have been further analyzed to assess their relative chemical instabilities while undergoing stepped chemical delithiation. Each system takes increasing amounts of protons at lower lithium contents. The differences are attributed to the relative chemical instabilities of the various cathodes that could be related to the position of the transition metal band and the top of the O2-:2p band. Chemically delithiated layered Li[Li0.17Mn0.33Co 0.5-yNiy]O 2 cathodes have also been characterized. The first charge and discharge capacities decrease with increasing nickel content. The decrease in the capacity with increasing nickel content is due to a decrease in the lithium content present in the transition metal layer and a consequent decrease in the amount of oxygen irreversibly lost during the first charge.

Investigation of Some Metals in Leaves and Leaf Extracts of Lippia javanica: Its Daily Intake

PubMed Central

Florence, Kunsamala

2017-01-01

Consumption of plant extracts can be a source of essential elements or a route of human exposure to toxicants. Metal concentrations in leaves, leaf brew, and infusion of L. javanica collected from five sites were determined by atomic absorption spectrometry after acid and aqueous extraction. Estimated daily intakes of metals in extracts were compared with recommended dietary allowances. Total metal concentrations in leaves varied with sampling sites (p < 0.05): Mn > Fe > Cu > Cr > Pb for sites SS2–SS5. The highest metal concentrations in leaves were recorded for SS3 (Cu: 15.32 ± 4.53 and Mn: 734.99 ± 105.49), SS5 (Fe: 210.27 ± 17.17), SS2 (Pb: 3.11 ± 0.21), and SS4 (Cr: 4.40 ± 0.75 mg/kg). Leaf infusion appeared to release higher Cu and Mn concentrations in leaves across sites (Cu: 21.65; Mn: 28.01%) than leaf brew (Cu: 11.95; Mn: 19.74%). Lead was not detected in leaf extracts. Estimated dietary intakes of Cr, Cu, Fe, and Mn were below recommended dietary allowances. A 250 ml cup of leaf infusion contributed 0.30–1.18% Cu and 4.46–13.83% Mn to the recommended dietary allowances of these elements per day. Lead did not pose any potential hazard when consumed in tea beverage made from brew and infusion of leaves of L. javanica. PMID:28781598

First X-ray crystal structure and internal reference diffusion-ordered NMR spectroscopy study of the prototypical Posner reagent, MeCu(SPh)Li(THF)3.

PubMed

Bertz, Steven H; Hardin, Richard A; Heavey, Thomas J; Jones, Daniel S; Monroe, T Blake; Murphy, Michael D; Ogle, Craig A; Whaley, Tara N

2013-07-29

Grow slow: The usual direct treatment of MeLi and CuSPh did not yield X-ray quality crystals of MeCu(SPh)Li. An indirect method starting from Me2CuLi⋅LiSPh and chalcone afforded the desired crystals by the slow reaction of the intermediate π-complex (see scheme). This strategy produced the first X-ray crystal structure of a Posner cuprate. A complementary NMR study showed that the contact ion pair was also the main species in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Internal energy transfer phenomenon and light-emission properties of γ-LiAlO2 phosphor doped with Mn2+

NASA Astrophysics Data System (ADS)

Wang, Bai-Bin; Chang, Chi-Fen; Yang, Wein-Duo

2013-07-01

γ-LiAlO2:Mn2+ phosphor was synthesized using the cellulose-citric acid sol-gel method, and its light emission and energy transfer properties were investigated. Excitation and emission spectrum analysis revealed a decrease in intensity of the spectrum as the amount of Mn2+ doping increased. Blasse's equation determined the maximum distance for energy transfer between Mn2+ ions as 4.3142 nm. Dexter's theory verifies that the mechanism of energy transfer between Mn2+ ions conforms to an electric dipole and electric quadrupole interaction.

Radiolabeled, Antibody-Conjugated Manganese Oxide Nanoparticles for Tumor Vasculature Targeted Positron Emission Tomography and Magnetic Resonance Imaging.

PubMed

Zhan, Yonghua; Shi, Sixiang; Ehlerding, Emily B; Graves, Stephen A; Goel, Shreya; Engle, Jonathan W; Liang, Jimin; Tian, Jie; Cai, Weibo

2017-11-08

Manganese oxide nanoparticles (Mn 3 O 4 NPs) have attracted a great deal of attention in the field of biomedical imaging because of their ability to create an enhanced imaging signal in MRI as novel potent T 1 contrast agents. In this study, we present tumor vasculature-targeted imaging in mice using Mn 3 O 4 NPs through conjugation to the anti-CD105 antibody TRC105 and radionuclide copper-64 ( 64 Cu, t 1/2 : 12.7 h). The Mn 3 O 4 conjugated NPs, 64 Cu-NOTA-Mn 3 O 4 @PEG-TRC105, exhibited sufficient stability in vitro and in vivo. Serial positron emission tomography (PET) and magnetic resonance imaging (MRI) studies evaluated the pharmacokinetics and demonstrated targeting of 64 Cu-NOTA-Mn 3 O 4 @PEG-TRC105 to 4T1 murine breast tumors in vivo, compared to 64 Cu-NOTA-Mn 3 O 4 @PEG. The specificity of 64 Cu-NOTA-Mn 3 O 4 @PEG-TRC105 for the vascular marker CD105 was confirmed through in vivo, in vitro, and ex vivo experiments. Since Mn 3 O 4 conjugated NPs exhibited desirable properties for T 1 enhanced imaging and low toxicity, the tumor-specific Mn 3 O 4 conjugated NPs reported in this study may serve as promising multifunctional nanoplatforms for precise cancer imaging and diagnosis.

Cathode limited charge transport and performance of thin-film rechargeable lithium batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bates, J.B.; Hart, F.X.; Lubben, D.

1994-11-01

Several types of thin-film rechargeable batteries based on lithium metal anodes and amorphous V{sub 2}O{sub 5} (aV{sub 2}O{sub 5}), LiMn{sub 2}O{sub 4}, and LiCoO{sub 2} cathodes have been investigated in this laboratory. In all cases, the current density of these cells is limited by lithium ion transport in the cathodes. This paper, discusses sources of this impedance in Li-aV{sub 2}O{sub 5} and Li-LiMn{sub 2}O{sub 4} thin-film cells and their effect on cell performance.

Electrochemical and thermodynamic studies of the electrode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Bang, Hyun Joo

A series of graphite samples were tested for their electrochemical performance as anode material for lithium ion cells. Specially treated natural graphite samples showed good reversible capacities and relatively small irreversible capacity losses. The good performance of these samples can be explained by the low surface area associated with the rounded edges and absence of exfoliation due to the presence of the rhombohedral phase and defects in the grain boundaries. Graphitized cokes showed larger irreversible capacity losses while mesophase carbons showed lower reversible capacity. The treated natural graphite samples, especially LBG25 were found to be high performance, low cost anode materials for the lithium ion cells. The electrochemical and thermal behaviors of the spinels---LiMn 2O4, LiCo1/6Mn11/6O4, LiFe 1/6Mn11/6O4, and LiNi1/6Mn11/6 O4 were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge/discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention(GITT) was observed for the substituted spinels (0.11% loss/cycle for LiCo1/6Mn 11/6O4; 0.3% loss/cycle for LiFe1/6Mn11/6 O4; and 0.2% loss/cycle for LiNi1/6Mn11/6 O4) than for the lithium manganese dioxide spinel (1.6% loss/cycle for first 10 cycles, 0.9% loss/cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry (DSC) results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels. The thermal profile of LiMn2O4 and LiAl0.17 Mn1.83O3.97S0.03 was measured in an isothermal micro-calorimeter. The heat contributions are discussed in terms of reversible and irreversible heat generation, in combination with the entropy change directly obtained by the dE/dT measurements and the over-potential measurements. The endothermic and exothermic heat profiles observed during the charge and discharge processes are related to the Li insertion/extraction reaction in the spinel host structure for both materials. The reversible heat generation due to the lithium insertion/extraction reaction in the host electrode is estimated on the basis of the cell entropy change. The heat generation calculated from DeltaS and the open circuit potential results is consistent with the heat profile (exothermic/endothermic) generated during the charge/discharge process and with the magnitude of the heat generation from the experimental results obtained from the IMC at a slow charge/discharge rate. The irreversible heat generation dependence on the current rate is discussed at different discharge rates.

Electrochemical measurements of diffusion coefficients and activity coefficients for MnCl2 in molten eutectic LiCl-KCl

NASA Astrophysics Data System (ADS)

Horvath, D.; Rappleye, D.; Bagri, P.; Simpson, M. F.

2017-09-01

An electrochemical study of manganese chloride in molten salt mixtures of eutectic LiCl-KCl was carried out using a variety of electrochemical methods in a high temperature cell including cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA), and open circuit potentiometry. Single step reduction from Mn2+ to Mn(0) was observed on both W and Mo working electrodes. Using a combination of these methods, measurements were made of activity coefficient and diffusion coefficient for MnCl2 in LiCl-KCl as a function of concentration (3.54 × 10-4 to 3.60 × 10-3 mol fraction of MnCl2) at 773K. From OCP measurements, values for activity coefficient varied from 0.014 to 0.0071. Diffusion coefficients varied with concentration and differed based on measurement method (CV, CA, or CP). Based on cyclic Mn(II) ranged from 1.1 to 2.8 × 10-5 cm2/s depending on concentration.

PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Knight, Brandon M.

Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both the electrolyte solution and uncharged cathode particles were analyzed. The solid cathode particles were analyzed via scanning electron microscopy (SEM) whereas the electrolyte solution was analyzed using inductively coupled plasma mass spectroscopy (ICP-MS). The SEM analysis assists with elucidation of changes to the surfaces of the cathode particles. The ICP-MS of the electrolyte allows the determination of the extent of Mn and Ni dissolution. Samples of LiNi0.5Mn1.5O4 with different crystal surface facets were prepared to investigate the role of particle morphology in Mn and Ni dissolution. The factors affecting Mn and Ni dissolution and methods to inhibit dissolution will be discussed.

Passivating film artificially built on LiNi0.5Mn1.5O4 by molecular layer deposition of (pentafluorophenylpropyl)trimethoxysilane

NASA Astrophysics Data System (ADS)

Chae, Seulki; Soon, Jiyong; Jeong, Hyejeong; Lee, Tae jin; Ryu, Ji Heon; Oh, Seung M.

2018-07-01

In this study, (pentafluorophenylpropyl)trimethoxysilane (PFPPS) is grafted on a nickel-doped manganese spinel (LiNi0.5Mn1.5O4, LNMO) surface to suppress the failure modes in the 5-V positive electrode; electrolyte oxidation/film deposition, acid generation, and metal (Ni and Mn) dissolution. Vapor-phase molecular layer deposition is used to deposit a uniformly covered PFPPS layer on the LNMO surface. When the Li/LNMO cell is cycled at 3.5-4.9 V (vs. Li/Li+), the PFPPS moiety on the LNMO surface remains intact (not oxidized) under the highly oxidizing condition. Several beneficial features are observed with the PFPPS grafting. The oxidative electrolyte decomposition is mitigated, which increases the Coulombic efficiency of the Li/LNMO cell. Consequently, the surface film deposition and cell polarization are reduced, improving the capacity retention. Moreover, the acid generation and metal dissolution are also mitigated.

Coercivity enhancement in Mn-Al-Cu flakes produced by surfactant-assisted milling

NASA Astrophysics Data System (ADS)

Saravanan, P.; Hsu, Jen-Hwa; Vinod, V. T. P.; Černík, Miroslav; Kamat, S. V.

2015-11-01

We herein report the achievement of exceptionally high coercivity (Hc) values: 9.92 and 5.86 kOe at 5 and 300 K, respectively, for Mn55Al43Cu2 flakes produced by surfactant-assisted milling process without employing any heat-treatment. The use of surfactants such as oleic acid and oleylamine during milling yielded high-aspect ratio flakes for the Mn-Al-Cu alloy. Structural studies confirmed the presence of τ- and β-phases as the major constituents in the Mn-Al-Cu flakes. The observed Hc enhancement is due to the increase in anisotropy field and structural defects, which is hypothesized to originate from the domain-wall pinning as a consequence of precipitation of fine Cu-particles present at the grain boundaries.

Study on effects of powder and flake chemistry and morphology on the properties of Al-Cu-Mg-X-X-X powder metallurgy advanced aluminum alloys

NASA Technical Reports Server (NTRS)

Meschter, P. J.; Lederich, R. J.; Oneal, J. E.

1986-01-01

A study was conducted: (1) to develop rapid solidification processed (RSP) dispersoid-containing Al-3Cu-2Li-1Mg-0.2Zr alloys as substitutes for titanium alloys and commercial 2XXX aluminum alloys for service to at least 150 C; and (2) to develop RSP Al-4Li-Cu-Mg-Zr alloys as substitutes for high-strength commercial 7XXX alloys in ambient-temperature applications. RSP Al-3Cu-2Li-1Mg-0.2Zr alloys have density-normalized yield stresses at 150 C up to 52% larger than that of 2124-T851 and up to 30% larger than that of Ti-6Al-4V. Strength at 150 C in these alloys is provided by thermally stable delta' (Al3Li), T1 (Al2LiCu), and S' (Al2CuMg) precipitates. Density-normalized yield stresses of RSP Al-3Cu-2Li-1Mg-0.2Zr alloys are up to 100% larger than that of 2124-T851 and equivalent to that of Al-8Fe-4Ce at 260 C. Strength in the RSP alloys at 260 C is provided by incoherent dispersoids and subboundary constituent particles such as T1 and S. The RSP alloys are attractive substitutes in less than or = 100-h exposures for 2xxx and Al-4Fe-Ce alloys up to 260 C and for titanium alloys up to 150 C. RSP Al-4Li-Cu-Mg-Zr alloys have ambient-temperature yield and ultimate tensile stresses similar to that of 7050-T7651, and are 14% less dense. RSP Al-4Li-0.5Cu-1.5Mg-0.2Zr has a 20% higher specific yield stress, 40% higher specific elastic modulus, and superior corrosion resistance compared to the properties of 7050-T7651. Strength in the Al-4Li-Cu-Mg-Zr alloy class is primarily provided by the substructure and delta' precipitates and is independent of Cu:Mg ratio. Improvements in fracture toughness and transverse-orientation properties in both alloy classes depend on improved melt practices to eliminate oxide inclusions which are incorporated into the consolidated forms.

Structural implications for oxygen electrocatalysis in earthabundant transition metal oxides

NASA Astrophysics Data System (ADS)

Gardner, Graeme Patrick

Transition metal oxides and related nitrides/nitride-oxides represent a class of materials that have shown great promise as oxygen electrocatalysts to replace the otherwise non-scalable noble metal-based catalysts currently implemented in commercial technologies. That is, compounds in this class of materials have shown promise as electrocatalysts for both the oxygen evolution (OER) and oxygen reduction reactions (ORR). The two aforementioned half-reactions are at the cornerstone of most renewable energy transformations, as oxygen is an inherently practical and abundant source and sink for electrons. In water electrolysis to produce hydrogen, oxygen is inevitably formed, and in a fuel cell the driving force for extracting electrochemical energy from hydrogen is pairing it with the reduction of oxygen to water. If this can be accomplished reversibly, the problem of "transient" renewable energy and its storage can be mitigated. We have examined many metal oxides and related compounds based upon Earth- abundant transition metals (primarily first row) that are crystalline, yet high surface area, for these important electrocatalytic reactions, and found that crystal structure plays a crucial role in determining activity. In fact, while most studies on heterogeneous catalysis focus on the synthesis of defect-rich, high surface area, practically amorphous materials to elicit high activity, we have found that particular crystalline phases possess not only the appropriate activity, but to some degree more importantly, the stability to be named good catalysts. In Chapter 2, we demonstrate that of the two structural types of lithium cobalt oxide (LiCoO2) - layered (R-3m) and cubic (Fd-3m) - only the cubic phase is revealed to be an efficient and stable catalyst for OER. Whether water oxidation is driven photochemically, or electrochemically, the cubic phase LiCoO2 possessing a spinel-like structure (AB 2O4) with [Co4O4] subunits within the crystal is more active. It is seen that electrochemically, both the cubic and layered phases transform to the spinel LiCo2O4 at surface and subsurface levels. This coincides with partial delithiation that is more extensive in layered LiCoO2. It is revealed that the oxidation of CoMn3+ to Co4+ is accompanied by delithiation in aqueous electrolyte to form the active state of the LiCoO2 catalyst. The electronic properties of the cubic spinel allow for localization of electron holes at cubic core active sites to effect water oxidation, whereas holes are more extensively delocalized in layered LiCoO2 in concert with the Li+ deintercalation reaction. In Chapter 3, we investigate the influence of chemical composition on the catalytic water oxidation activity of Co-substituted spinel LiMn 2O4 and Mn-substituted cubic LiCoO2. We find that in the spinel LiMn2O4, CoMn3+ substitution occurs at the B-site for MnMn3+, and the solid solution limit for starts at 1:1 Co:Mn ratio, where Co begins to go into the A-site. The activity for OER increases with increasing Co, owing to the symmetrization of the M4O4 core structure (Jahn-Teller distortions suppressed), which allows for hole delocalization that enables CoMn 3+/4+ oxidation. The more positive redox potential of Co4+ makes for facile water oxidation. Substituting Mn for Co in cubic LiCoO2 allows for retention of MnMn3+, which has been correlated with water oxidation activity in many catalysts. The solid solution limit in this series is also near 1:1 at the B- site. However, the increase in Mn content corresponds to decreasing activity in both water oxidation and oxygen reduction, which correlates well with decreases in pre- catalytic oxidation and reduction peak yields. The results show replacement of CoMn 3+ with MnMn3+ effectively eliminates active sites. Therefore, MnMn3+ in this electronic and structural environment is not active, which agrees well with a recent literature report on corner- shared MnMn3+ octahedral being necessary to produce OER activity in Mn oxides. Finally, in chapter 4, bifunctional oxygen electrocatalysts are explored in depth with a series of cobalt-molybdenum oxides/nitrides. We demonstrate that CoMoN2, with relatively strong M-N interactions, has ideal electronic properties for ORR, and upon oxidation of the surface, yields an active OER catalyst. However, the surface oxidation is found to be irreversible and once oxidized, the activity for ORR significantly decreases. The surface both before and after catalysis was analyzed by XPS, which showed the suppression of Mo and N signals after exposure to OER conditions, meaning the active catalyst is a Co oxide of high valency (3/4+). The results from this study suggests truly reversible, bifunctional oxygen electrocatalysis may be obtained by designing a catalyst whose surface is only partly oxidized and/or can be reversibly reduced in the potential window relevant to OER and ORR.

27Al, 63Cu NMR spectroscopy and electrical transport in Heusler Cu-Mn-Al alloy powders

NASA Astrophysics Data System (ADS)

Nadutov, V. M.; Perekos, A. O.; Kokorin, V. V.; Trachevskii, V. V.; Konoplyuk, S. M.; Vashchuk, D. L.

2018-02-01

The ultrafine powder of the Heusler Cu-13,1Mn-12,6Al (wt.%) alloy produced by electrical spark dispersion (ESD) in ethanol and the pellets prepared by pressing of the powders and aged in various gas environment (air, Ar, vacuum) were studied by XRD, nuclear magnetic resonance, magnetic and electric transport methods. The constituent phases were identified as b.c.c. α-Cu-Mn-Al, f.c.c. γ-Cu-Mn-Al, Cu2MnAl, and oxides. The sizes of the coherently scattering domains (CSD) and the saturation magnetizations were in the range of 4-90 nm and 0-1.5 Am2/kg, respectively. 27Al and 63Cu NMR spectra of the powders and pellets have shown hyperfine structure caused by contributions from atomic nuclei of the constituent phases. The aging of pellets in different gas environments had effect on their phase composition but no effect on dispersion of the phases. In contrast to the as-cast alloy, electrical resistance of the pellets evidenced semiconducting behavior at elevated temperatures due to the presence of metal oxides formed on the surfaces of nanoparticles.

Exposure of women to trace elements through the skin by direct contact with underwear clothing.

PubMed

Nguyen, Thao; Saleh, Mahmoud A

2017-01-02

Heavy metals pose a potential danger to human health when present in textile materials. In the present study, inductive coupled plasma mass spectrometry (ICPMS) was used to determine the concentrations and the identity of extractable inorganic elements from different brands of women undergarments. A total of 120 samples consisting of 63 cottons, 44 nylons and 13 polyesters manufactured in 14 different countries having different colors were analyzed for their extractable metals contents. Elements analyzed were Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Ti, V and Zn. Cotton undergarments were rich in Al, Fe and Zn, nylon undergarments had high levels of Cr, Cu and Al, while polyester fabrics contained higher levels of Ni and Fe compared to cotton or nylon. With respect to manufacturing countries, China, Egypt and India showed the highest concentrations of metals in all fabrics. With respect to the color, black garments were characteristic by high concentration of Fe, blue colors with Cu, brown garments with Fe and Cu, green garments with Cu and Fe, pink garments with Al, purple garments with Al and Cu and red garments with Cr, Zn and Al. The consumer should be made aware of the potential dangers of these metals in their clothing.

Geochemistry of ferromanganese nodule-sediment pairs from Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2011-01-01

Fourteen ferromanganese nodule-sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule-sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo - (307, 273), Ni - (71, 125), Mn - (64, 87), Cu - (43, 80), Co - (23, 75), Pb - (15, 24), Zn - (9, 11) and V - (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation ( r ⩾ 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.

Improvement of the overall performances of LiMn{sub 2}O{sub 4} via surface-modification by polypyrrole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Ting; Wang, Wan; Zhu, Ding

2015-11-15

Graphical abstract: Polypyrrole(PPy) film has improved the rate performance of LiMn{sub 2}O{sub 4} efficiently due to its excellent conductivity. PPy@LiMn{sub 2}O{sub 4} could provide more energy under the higher power than pristine LMO. - Highlights: • The PPy layer on the surface of LMO particles hasn’t been studied in LiMn{sub 2}O{sub 4} so far. • The solvent in the synthesis process of PPy@LMO is absolute ethyl alcohol. • The differences of surface-modification between the PPy and PI for LMO. • The analyses of rate performances are through specific power. - Abstract: Polypyrrole (PPy) is an excellent conductive polymer and themore » study on its utilization in the surface modification of the LiMn{sub 2}O{sub 4} (LMO) is few. In this work, the structure, morphology and electrochemical performance of surface-modified LiMn{sub 2}O{sub 4} composites with PPy and polyimides (PI) were discussed. The crystal structure, chemical bonds and morphology were characterized through X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), respectively. Moreover, the specific power and cycling performance were tested at room and high (55 °C) temperature. The PPy@LMO (surface-modified LMO composites with PPy) shows better performances than the pristine LMO. The addition of PPy not only weakens the corrosion caused by electrolyte, but also improves the discharge capacity at higher rates. The charge transfer resistance of the PPy@LMO is much lower than that of the pristine LMO after cycling.« less

[Study on the determination of trace Cu and Mn in foodstuff preconcentration by precipitate flotation and FAAS].

PubMed

Li, Chun-xiang; Chen, Ting-yu; Yan, Yong-sheng

2007-10-01

In the present paper, the use of 8-hydroxyquinoline(oxine, HQ) complexs in precipitate flotation to separate and preconcentrate Cu and Mn, using SDBS as collector, followed by AAS spectrophotometric determination is proposed. The optimum conditions of precipitate flotation were studied. The effects of several parameters of flotation processes condition on single metal ions precipitation-flotation and multi-metal ions coprecipitation-flotation of Cu and Mn at pH 9 were investigated. The experimental results show that the flotation rate of Cu is supreme with pH 9. Under the condition of pH 9 and changing the ratio of concentration, when Mn/Cu> or =8, the recovery rate of Cu is less than 90%. This method is simple, rapid, accurate, sensitive and precise and avoids using the virulent organic solvent. The linear range of Cu is 0.5-5.0 microg x mL(-1) with the correlative coefficient of 0.9996, detection limit of this method was found to be 1.59 x 10(-3) microg x mL(-1), the linear range of Mn is 0.5-5.0 microg x mL(-1) with the correlative coefficient of 0.9987, and the detection limit of this method was found to be 3.52 x 10(-3) microg x mL(-1). The method was applied to the determination of Cu and Mn in foodstuff, and the recovery is 87.6%-100.7%. The result was satisfactory.

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ya; Cui, Yan; Zuo, Xiaoxi

2014-10-15

Highlights: • The spent Zn–Mn batteries collected from manufacturers is the target waste. • A facile reclaiming process is presented. • The zinc is reclaimed to valuable electrolytic zinc by electrodepositing method. • The manganese elements are to produce valuable LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} battery material. • The reclamation process features environmental friendliness and saving resource. - Abstract: A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organicmore » separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H{sub 2}SO{sub 4} (2 mol L{sup −1}) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37–40 °C and 300 A m{sup −2}. The most of MnO{sub 2} and a small quantity of electrolytic MnO{sub 2} are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} material of lithium-ion battery. The as-synthesized LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} discharges 118.3 mAh g{sup −1} capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO{sub 2}. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.« less

Replacement of a cytosolic copper/zinc superoxide dismutase by a novel cytosolic manganese superoxide dismutase in crustaceans that use copper (haemocyanin) for oxygen transport.

PubMed Central

Brouwer, Marius; Hoexum Brouwer, Thea; Grater, Walter; Brown-Peterson, Nancy

2003-01-01

The blue crab, Callinectes sapidus, which uses the copper-dependent protein haemocyanin for oxygen transport, lacks the ubiquitous cytosolic copper-dependent enzyme copper/zinc superoxide dismutase (Cu,ZnSOD) as evidenced by undetectable levels of Cu,ZnSOD activity, protein and mRNA in the hepatopancreas (the site of haemocyanin synthesis) and gills. Instead, the crab has an unusual cytosolic manganese SOD (cytMnSOD), which is retained in the cytosol, because it lacks a mitochondrial transit peptide. A second familiar MnSOD is present in the mitochondria (mtMnSOD). This unique phenomenon occurs in all Crustacea that use haemocyanin for oxygen transport. Molecular phylogeny analysis suggests the MnSOD gene duplication is as old as the origin of the arthropod phylum. cytMnSOD activity in the hepatopancreas changes during the moulting cycle of the crab. Activity is high in intermoult crabs and non-detectable in postmoult papershell crabs. mtMnSOD is present in all stages of the moulting cycle. Despite the lack of cytCu,ZnSOD, crabs have an extracellular Cu,ZnSOD (ecCu,ZnSOD) that is produced by haemocytes, and is part of a large, approx. 160 kDa, covalently-linked protein complex. ecCu,ZnSOD is absent from the hepatopancreas of intermoult crabs, but appears in this tissue at premoult. However, no ecCu,ZnSOD mRNA can be detected, suggesting that the protein is recruited from the haemolymph. Screening of different taxa of the arthropod phylum for Cu,ZnSOD activity shows that those crustaceans that use haemoglobin for oxygen transport have retained cytCu,ZnSOD. It appears, therefore, that the replacement of cytCu,ZnSOD with cytMnSOD is part of an adaptive response to the dynamic, haemocyanin-linked, fluctuations in copper metabolism that occur during the moulting cycle of the crab. PMID:12769817

Contamination of the Conchos River in Mexico: does it pose a health risk to local residents?

PubMed

Rubio-Arias, Hector; Quintana, César; Jimenez-Castro, Jorge; Quintana, Ray; Gutierrez, Melida

2010-05-01

Presently, water contamination issues are of great concern worldwide. Mexico has not escaped this environmental problem, which negatively affects aquifers, water bodies and biodiversity; but most of all, public health. The objective was to determine the level of water contamination in six tributaries of the Conchos River and to relate their levels to human health risks. Bimonthly samples were obtained from each location during 2005 and 2006. Physical-chemical variables (temperature, pH, electrical conductivity (EC), Total solids and total nitrogen) as well as heavy metals (As, Cr, Cu, Fe, Mn, Ni, V, Zn, and Li) were determined. The statistical analysis considered yearly, monthly, and location effects, and their interactions. Temperatures differed only as a function of the sampling month (P < 0.001) and the pH was different for years (P = 0.006), months (P < 0.001) and the interaction years x months (P = 0.018). The EC was different for each location (P < 0.001), total solids did not change and total nitrogen was different for years (P < 0.001), months (P < 0.001) and the interaction years x months (P < 0.001). The As concentration was different for months (P = 0.008) and the highest concentration was detected in February samples with 0.11 mg L(-1). The Cr was different for months (P < 0.001) and the interaction years x months (P < 0.001), noting the highest value of 0.25 mg L(-1). The Cu, Fe, Mn, Va and Zn were different for years, months, and their interaction. The highest value of Cu was 2.50 mg L(-1); for Fe, it was 16.36 mg L(-1); for Mn it was 1.66 mg L(-1); V was 0.55 mg L(-1); and Zn was 0.53 mg L(-1). For Ni, there were differences for years (P = 0.030), months (P < 0.001), and locations (P = 0.050), with the highest Ni value being 0.47 mg L(-1). The Li level was the same for sampling month (P < 0.001). This information can help prevent potential health risks in the communities established along the river watershed who use this natural resource for swimming and fishing. Some of the contaminant concentrations found varied from year to year, from month to month and from location to location which necessitated a continued monitoring process to determine under which conditions the concentrations of toxic elements surpass existing norms for natural waters.

Contamination of the Conchos River in Mexico: Does It Pose a Health Risk to Local Residents?

PubMed Central

Rubio-Arias, Hector; Quintana, César; Jimenez-Castro, Jorge; Quintana, Ray; Gutierrez, Melida

2010-01-01

Presently, water contamination issues are of great concern worldwide. Mexico has not escaped this environmental problem, which negatively affects aquifers, water bodies and biodiversity; but most of all, public health. The objective was to determine the level of water contamination in six tributaries of the Conchos River and to relate their levels to human health risks. Bimonthly samples were obtained from each location during 2005 and 2006. Physical-chemical variables (temperature, pH, electrical conductivity (EC), Total solids and total nitrogen) as well as heavy metals (As, Cr, Cu, Fe, Mn, Ni, V, Zn, and Li) were determined. The statistical analysis considered yearly, monthly, and location effects, and their interactions. Temperatures differed only as a function of the sampling month (P < 0.001) and the pH was different for years (P = 0.006), months (P < 0.001) and the interaction years x months (P = 0.018). The EC was different for each location (P < 0.001), total solids did not change and total nitrogen was different for years (P < 0.001), months (P < 0.001) and the interaction years x months (P < 0.001). The As concentration was different for months (P = 0.008) and the highest concentration was detected in February samples with 0.11 mg L−1. The Cr was different for months (P < 0.001) and the interaction years x months (P < 0.001), noting the highest value of 0.25 mg L−1. The Cu, Fe, Mn, Va and Zn were different for years, months, and their interaction. The highest value of Cu was 2.50 mg L−1; for Fe, it was 16.36 mg L−1; for Mn it was 1.66 mg L−1; V was 0.55 mg L−1; and Zn was 0.53 mg L−1. For Ni, there were differences for years (P = 0.030), months (P < 0.001), and locations (P = 0.050), with the highest Ni value being 0.47 mg L−1. The Li level was the same for sampling month (P < 0.001). This information can help prevent potential health risks in the communities established along the river watershed who use this natural resource for swimming and fishing. Some of the contaminant concentrations found varied from year to year, from month to month and from location to location which necessitated a continued monitoring process to determine under which conditions the concentrations of toxic elements surpass existing norms for natural waters. PMID:20623012

Surface Reactivity of Li2MnO3: First-Principles and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence; Vallverdu, Germain; Allouche, Joachim; Charles-Blin, Youn; Chotard, Jean-Noël; Ménétrier, Michel; Baraille, Isabelle

2017-12-20

This article deals with the surface reactivity of (001)-oriented Li 2 MnO 3 crystals investigated from a multitechnique approach combining material synthesis, X-ray photoemission spectroscopy (XPS), scanning electron microscopy, Auger electron spectroscopy, and first-principles calculations. Li 2 MnO 3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO 2 gas molecules on large Li 2 MnO 3 crystals to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after SO 2 adsorption show in particular that the adsorption is homogeneous at the micro- and nanoscale and involves Mn reduction, whereas first-principles calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.

Recycling metals from lithium ion battery by mechanical separation and vacuum metallurgy.

PubMed

Xiao, Jiefeng; Li, Jia; Xu, Zhengming

2017-09-15

The large-batch application of lithium ion batteries leads to the mass production of spent batteries. So the enhancement of disposal ability of spent lithium ion batteries is becoming very urgent. This study proposes an integrated process to handle bulk spent lithium manganese (LiMn 2 O 4 ) batteries to in situ recycle high value-added products without any additives. By mechanical separation, the mixed electrode materials mainly including binder, graphite and LiMn 2 O 4 are firstly obtained from spent batteries. Then, the reaction characteristics for the oxygen-free roasting of mixed electrode materials are analyzed. And the results show that mixed electrode materials can be in situ converted into manganese oxide (MnO) and lithium carbonate (Li 2 CO 3 ) at 1073K for 45min. In this process, the binder is evaporated and decomposed into gaseous products which can be collected to avoid disposal cost. Finally, 91.30% of Li resource as Li 2 CO 3 is leached from roasted powders by water and then high value-added Li 2 CO 3 crystals are further gained by evaporating the filter liquid. The filter residues are burned in air to remove the graphite and the final residues as manganous-manganic oxide (Mn 3 O 4 ) is obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

High resolution electron microscopy study of a high Cu variant of Weldalite (tm) 049 and a high strength Al-Cu-Ag-Mg-Zr alloy

NASA Technical Reports Server (NTRS)

Herring, R. A.; Gayle, Frank W.; Pickens, Joseph R.

1991-01-01

Weldalite (trademark) 049 is an Al-Cu-Li-Ag-Mg alloy that is strengthened in artificially aged tempers primarily by very thin plate-like precipitates lying on the set of (111) matrix planes. This precipitate might be expected to be the T(sub 1) phase, Al2CuLi, which has been observed in Al-Cu-Li alloys. However, in several ways this precipitate is similar to the omega phase which also appears as the set of (111) planes plates and is found in Al-Cu-Ag-Mg alloys. The study was undertaken to identify the set of (111) planes precipitate or precipitates in Weldalite (trademark) 049 in the T8 (stretched and artificially aged) temper, and to determine whether T(sub 1), omega, or some other phase is primarily responsible for the high strength (i.e., 700 MPa tensile strength) in this Al-Cu-Li-Ag-Mg alloy.

Reaction mechanism and thermal stability study on cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Fang, Jin

Olivine-type lithium iron phosphate has been a very promising cathode material since it was proposed by Padhi in 1997, low-cost, environmental friendly and stable structure ensure the commercialization of LiFePO 4. In LiFePO4, during charge and discharge process, Li ions are transferred between two phases, Li-poor LialphaFePO 4 and Li-rich Li1-betaFePO4, which implies a significant energy barrier for the new phase nucleation and interface growth, contrary to the fast reaction kinetics experimentally observed. The understanding of the lithiation and delithiation mechanism of this material has spurred a lot of research interests. Many theory models have been proposed to explain the reaction mechanism of LiFePO4, among them, the single phase model claims that the reaction goes through a metastable single phase, and the over potential required to form this single phase is about 30mV, so we studied the driving force to transport lithium ions between Lialpha FePO4 and Li1-betaFePO4 phases and compared the particle sizes effect. Experiment results shows that, the nano-sized (30nm) LiFePO4 has wider solid solution range, lower solid solution formation temperature and faster kinetics than normal LiFePO4 (150nm). Also a 20mV over potential was observed in both samples, either after relaxing the FePO4/LiFePO4 system to equilibrium or transport lithium from one side to the other side, the experiment result is corresponding to theoretical calculation; indicates the reaction might go through single-phase reaction mechanism. The energy and power density of lithium ion battery largely depend on cathode materials. Mn substituted LiFePO4 has a higher voltage than LiFePO4, which results a higher theoretical energy density. Safety issue is one of the most important criterions for batteries, since cathode materials need to maintain stable structure during hundreds of charge and discharge cycles and ranges of application conditions. We have reported that iron-rich compound o-Fe1-yMnyPO4 (0≤y≤0.4) is stable up to 600 °C with particle size above 100 nm particle. And in this work Mn rich olivine phase Fe1-yMnyPO4 is found to be thermally stable up to at least 450 °C with particle size down to below 50 nm, different delithiation methods result in different decomposition routes, electrochemical delithiation results in decreased thermal stability. Moisture exposure appears the most detrimental to the thermal stability of Mn-rich samples. LiNi0.5Mn1.5O4 has attracted a lot of attentions because the potential is even higher (˜ 4.7 V vs Li +/Li0). However, electrolyte decomposition is quite often observed during electrochemistry cycles due to the high voltage operation window. Spinel LiNi0.5Mn1.5O4 is known as ordered and disordered according to the distribution of cations which relates to the synthesis conditions. Mn and Ni ions distribute either randomly in 16d sites of an Fd3m-space group or ordered in 4a and 12d sites of P4332 space group. During discharge and charge processes, Li ions insert and extract from the structure with the oxidation state of Ni changing between +2 and +4 while Mn remains as Mn4+. So far the correlation between cation distribution and electrochemical performance is still unclear, mostly the disordered samples are observed to have better rate capabilities. In order to study the reaction mechanism, combined XRD and XAS are used to investigate the oxidation state of transition metals and structure change of LiNi0.5Mn1.5O4 during electrochemical cycling, disordered and ordered samples were compared and studied, and both samples show three phases transformation during charge and discharge. However, the samples suffer from severe electrolyte decomposition which has influence on the results. Good spinel samples with nice electrochemistry performance is required, pure spinel samples are obtained by using co-precipitation method, the distribution of transition metal ions can be controlled by controlling the synthesis temperature, and electrolyte plays an important role in the electrochemistry performance of spinel LiNi0.5Mn1.5O 4.

Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

DOE PAGES

Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; ...

2015-10-05

The electronic and electrochemical properties of the high-voltage spinel LiMn 1.5Ni 0.5O 4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni 2+/ 3+. and Ni 3+/ 4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 inmore » Li Li 1-xMn 1.5Ni 0.5O 4. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn 1.5Ni 0.5O 4 to Li 0.5Mn 1.5Ni 0.5O 4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn 3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.« less

Engineering hierarchical Diatom@CuO@MnO2 hybrid for high performance supercapacitor

NASA Astrophysics Data System (ADS)

Zhang, Yan; Guo, Wan Wan; Zheng, Tian Xu; Zhang, Yu Xin; Fan, Xing

2018-01-01

A rational and hierarchical Diatom@CuO@MnO2 hybrid was fabricated via a facile electroless copper plating technology, following by a one-pot hydrothermal reaction with KMnO4. Such unique architecture acts as a supercapacitor electrode, which exhibits a high specific capacitance (240 F g-1 at a current density of 0.5 A g-1), good rate capability (58.3% retention when the current density increases from 0.5 to 5 A g-1), and excellent electrochemical cycling stability (91.2% retention of the initial specific capacitance after 4000 cycles at a current density of 2 A g-1). The impressive electrochemical performance of this Diatom@CuO@MnO2 electrode ascribed to the synergistic effect between the CuO particles and MnO2 nanosheets. Therefore, it can be expected that this unique Diatom@CuO@MnO2 electrode may have great promise for the application in supercapacitors.

Effect of sputtering condition and heat treatment in Co/Cu/Co/FeMn spin valve

NASA Astrophysics Data System (ADS)

Kim, Hong Jin; Bae, Jun Soo; Lee, Taek Dong; Lee, Hyuck Mo

2002-03-01

The exchange field of Cu(50 Å)/FeMn(50 Å)/Co(50 Å) sputtered on Si substrate was studied in terms of surface roughness and phase formation of γ-FeMn under a variety of Ar pressures and powers in sputtering. It was found that the exchange field is stronger when the surface is smoother and the FeMn layer forms better. The exchange bias field increased by more than three times after heat treatment. The effect of heat treament on magnetoresistance (MR) and resistance of the top spin valve, substrate/Co(30 Å)/Cu(30 Å)/Co(30 Å)/FeMn(150 Å), was studied. It was observed that the MR started to increase with annealing temperature and the effect was significant at 150°C. The heat treatment led to the disappearance of the intermixed layer between Co and Cu, and the concentration profile of Cu became flat and smooth at this temperature.

Impact of a long term fire retardant (Fire Trol 931) on the leaching of Na, Al, Fe, Mn, Cu and Si from a Mediterranean forest soil: a short-term, lab-scale study.

PubMed

Koufopoulou, Sofia; Michalopoulos, Charalampos; Tzamtzis, Nikolaos; Pappa, Athina

2014-06-01

Long term fire retardant (LTR) application for forest fire prevention purposes as well as wildland fires can result in chemical leaching from forest soils. Large quantities of sodium (Na), aluminium (Al), iron (Fe), manganese (Mn), copper (Cu) and silicon (Si) in leachates, mainly due to ammonium (one of the major LTR components) soil deposition, could affect the groundwater quality. The leaching of Na, Al, Fe, Mn, Cu and Si due to nitrogen based LTR application (Fire Trol 931) was studied at laboratory scale. The concentrations of Na(+), Al(3+), Fe(3+)/Fe(2+), Mn(2+), Cu(2+) and Si(4+) were measured in the resulting leachates from pots with forest soil and pine trees alone and in combination with fire. The leaching of Na, Fe and Si from treated pots was significantly greater than that from control pots. The leaching of Al, Mn and Cu was extremely low.

Substitution of Li for Cu in Cu2ZnSnS4: Toward Wide Band Gap Absorbers with Low Cation Disorder for Thin Film Solar Cells.

PubMed

Lafond, A; Guillot-Deudon, C; Vidal, J; Paris, M; La, C; Jobic, S

2017-03-06

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

Surface characterization of ZnO/ZnMn2O4 and Cu/Mn3O4 powders obtained by thermal degradation of heterobimetallic complexes

NASA Astrophysics Data System (ADS)

Barrault, Joël; Makhankova, Valeriya G.; Khavryuchenko, Oleksiy V.; Kokozay, Vladimir N.; Ayrault, Philippe

2012-03-01

From the selective transformation of the heterometallic (Zn-Mn or Cu-Mn) carboxylate complexes with 2,2'-bipyridyl by thermal degradation at relatively low (350 °C) temperature, it was possible to get either well defined spinel ZnMn2O4 over zinc oxide or well dispersed copper particles surrounded by a manganese oxide (Mn3O4) in a core-shell like structure. Morphology of the powder surface was examined by scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Surface composition was determined by X-ray photoelectron spectroscopy (XPS). Specific surface of the powders by nitrogen adsorption was found to be 33±0.2 and 9±0.06 m2 g-1 for Zn-Mn and Cu-Mn samples, respectively, which is comparable to those of commercial products.

Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel

DOE PAGES

Benedek, Roy

2017-09-18

Dissolution of Mn from lithium-manganese spinel has hindered its commercialization as a cathode material in Li-ion batteries. Disproportionation of near-surface Mn(III), in the presence of acid, has been widely thought to result in dissolved divalent Mn. To what extent stray acidic water in the cell (as opposed to the organic electrolyte) acts as the solvent for Mn ions has not been established. Simulations by Leung show that a small displacement of trivalent Mn from its equilibrium site at an LiMn 2O 4 (001)/ ethylene carbonate interface leads to its reduction to Mn(II). In the present work, Thermodynamic Integration is performed,more » based on first-principles molecular dynamics simulations within the Blue-Moon ensemble, for the detachment of Mn(III) ions at the LiMn 2O 4 (001)/water interface. The results show that reduction of Mn(III) to Mn(II) occurs also in the case of an aqueous interface. The simulations were performed for both neutral and acidic water (in the presence of HF), with the coordination number of the dissolving Mn ion with substrate oxygen ions taken as the reaction coordinate. The simulations indicate that an F - ion strongly binds to a surface Mn(III) ion, and weakens its adhesion to the substrate. Owing to this weakening, a surface Mn-F complex traverses regions of phase space at room temperature where disproportionation becomes energetically favorable. Although this disproportionation occurs close to the substrate, where the Mn coordination number is only slightly lowered from its equilibrium value, we argue that the likelihood of reattachment after disproportionation is small (Leung arrived at a similar interpretation in the case of the LiMn 2O 4 (001)/ EC interface). We suggest that the critical role of F - in promoting dissolution is to weaken the Mn binding to the substrate so as to enable disproportionation. The partially detached MnF complex may then undergo additional interaction with the solvent to form, e.g., MnF 2, which would enable transport away from the substrate. In conclusion, the EPR measurements by Shilina et al. which appear to show Mn(III) as the predominant solvated species are discussed.« less

Superoxide radical anion scavenging and dismutation by some Cu2+ and Mn2+ complexes: A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Joshi, Ravi

2017-10-01

Copper (Cu) and manganese (Mn) ions are catalytic centers, in complexed form, in scavenging and dismutation process of superoxide radicals anion (O2.-) by superoxide dismutase enzyme. In the present work, fast reaction kinetics and mechanism of scavenging and dismutation of O2.- by Cu2+, Mn2+ and their complexes formed with some natural ligands have been studied using pulse radiolysis technique. Catechol, gentisic acid, tetrahydroxyquinone, tyrosine, tryptophan, embelin and bilirubin have been used as low molecular weight natural ligands for Cu2+ and Mn2+ to understand superoxide radical scavenging and dismutation reactions. These complexes have been found to be efficient scavengers of O2.- (k 107-109 M-1 s-1). The effects of nature of metal ion and ligand, and stoichiometry of complex on scavenging reaction rate constants are reported. Higher scavenging rate constants have been observed with complexes of: (1) Cu2+ as compared to Mn2+, and (2) at [ligand]/[metal] ratio of one as compared to two. A clear evidence of O2.- dismutation by free metal ions and some of the complexes has been observed. The study suggests that complexes of Cu2+ and Mn2+ with small natural ligands can also act as SOD mimics.

Sol gel synthesis and characterization studies of Cupromanganite CaCu3Mn4O12

NASA Astrophysics Data System (ADS)

Nurulhuda, A.; Warikh, A. R. M.; Hafizzal, Y.

2017-08-01

A single-phase CaCu3Mn4O12 electroceramic had been prepared via sol gel method and fairly well densified at relative low temperature under atmospheric condition where the crystallization of CaCu3Mn4O12 occurred due to amorphous polymeric mixture. The precursor was prepared by mixing the solutions with 0.6 M citric acid (C6H8O7) as a chelating reagent with the mol ratio 1:2. The precursor gel formed was calcined and sintered at range 400 °C to 800°C by varying dwell time. Material formations under the reported conditions have been confirmed by X-ray diffraction (XRD). The results show that the formation of CaCu3Mn4O12 started at 500 ° C and was formed completely at 700 ° C for 18 hours. The microstructure of all CaCu3Mn4O12 was analysed using field emission scanning electron microscopy (FESEM). A smaller particle size with higher grain boundary was obtained at sintering 700°C to 800°C. FESEM results show the significant influence of calcinations and sintering parameter on the microstructure behaviour of CaCu2Mn4O12.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Örnek, Ahmet, E-mail: ahmetornek@kafkas.edu.tr; Can, Mustafa; Yeşildağ, Ali

Nanostructured LiCo{sub 1−x}Mn{sub x}PO{sub 4}/C (x = 0 and 0.05) materials were successfully produced as superior quality cathodes by combined sol-gel and carbothermal reduction methods. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma (ICP), cyclic voltammetry (CV) and galvanostatic measurements were applied to determine the phase purity, morphology and electrochemical qualifications. HR-TEM analysis reveals that the thickness of the surface carbon layer of 5 to 10 nm range with the uniform distribution. LiCo{sub 0·95}Mn{sub 0·05}PO{sub 4}/C particles were betweenmore » 40 and 80 nm and the same material exhibits a higher and stable reversible capacity (140 mA h g{sup −1}) with the long voltage plateau (4.76 V). Substitution of Co{sup 2+} with Mn{sup 2+} in LiCoPO{sub 4}/C has an influence on the initial discharge capacity and excellent cycling behaviour. The obtained results have attributed that production dynamics in nano-synthesis, the coating process with proper carbon source and an effective doping represent three parameters to prepare favorable cathode materials. - Highlights: • Structural, morphological and electrochemical effects of Mn doped LiCo{sub 1−x}Mn{sub x}PO{sub 4}–C electrodes are investigated. • Cheap, effective and simple sol-gel assisted carbothermal reduction approach is used. • After 60th cycle, capacity retention is almost 92% for LiCo{sub 0·95}Mn{sub 0.05}PO{sub 4}–C electrode. • Mn-doped sample exhibits distinctive oxidation (4.76 V and 4.12 V) peaks.« less

Advanced Nanofiber-Based Lithium-Ion Battery Cathodes

NASA Astrophysics Data System (ADS)

Toprakci, Ozan

Among various energy storage technologies, rechargeable lithium-ion batteries have been considered as effective solution to the increasing need for high-energy density electrochemical power sources. Rechargeable lithium-ion batteries offer energy densities 2 - 3 times and power densities 5 - 6 times higher than conventional Ni-Cd and Ni-MH batteries, and as a result, they weigh less and take less space for a given energy delivery. However, the use of lithium-ion batteries in many large applications such as electric vehicles and storage devices for future power grids is hindered by the poor thermal stability, relatively high toxicity, and high cost of lithium cobalt oxide (LiCoO2) powders, which are currently used as the cathode material in commercial lithium-ion batteries. Recently, lithium iron phosphate (LiFePO 4) powders have become a favorable cathode material for lithium-ion batteries because of their low cost, high discharge potential (around 3.4 V versus Li/Li+), large specific capacity (170 mAh g -1), good thermal stability, and high abundance with the environmentally benign and safe nature. As a result, there is a huge demand for the production of high-performance LiFePO4. However, LiFePO4 also has its own limitation such as low conductivity (˜10-9 S cm -1), which results in poor rate capability. To address this problem, various approaches can be used such as decreasing particle size of LiFePO 4, doping LiFePO4 with metal ions or coating LiFePO 4 surface with carboneous materials. Formation of conductive layer on LiFePO4 and decreasing particle size are promising approaches due to their superior contribution to electrical conductivity and electrochemical performance of LiFePO4. Although different approaches can be used for surface coating and particle size decrement, electrospinning can be potentially considered as an efficient, simple and inexpensive way. In this study, LiFePO 4/carbon and carbon nanotube- and graphene-loaded electrospun LiFePO 4/carbon composite nanofibers were synthesized by using a combination of sol-gel and electrospinning. During the material preparation, polyacrylonitrile (PAN) was used as an electrospinning media and a carbon source. LiFePO 4 precursor materials and/or conductive materials (carbon nanotubes and graphene) and PAN were dissolved in N,N-dimethylformamide separately and they were mixed before electrospinning. LiFePO4 precursor/PAN fibers were heat treated, during which LiFePO4 precursor transformed to energy-storage LiFePO4 material and PAN was converted to carbon. The surface morphology, microstructure and electrochemical performance of the materials were analyzed. Compared with conventional powder based positive electrodes, the novel LiFePO4/C composite nanofiber cathodes possess better electrochemical performance. Furthermore, the newly developed LiFePO 4/C composite nanofibers are easy to fabricate, highly controllable, and can be used in practical Lithium-ion battery applications. In addition to LiFePO4, more recent efforts have been directed to mixed form of layered lithiummetal oxides (Li-Ni-Mn-Co). Nickel and manganese are of importance because of their lower cost, safety and higher abundance in nature. These new cathodes offer noticeable improvement in the capacity and cycling behavior. In these cathodes, LiNi1/3Co1/3Mn 1/3O2 attracted significant interest because of its good electrochemical properties such as high capacity, prolonged cycling life, and so on. On the other hand, it has some disadvantages such as instability at high voltages and high current densities. To overcome these problems, synthesis of layered Li-rich composite materials such as xLi2MnO3˙(1-x)LiCo 1/3Ni1/3Mn1/3O2 can be a promising approach. In this study, various xLi2MnO3˙(1-x)LiCo 1/3Ni1/3Mn1/3O2 (x=0.1, 0.2, 0.3, 0.4, 0.5) composite cathode materials were prepared by a one-step sol-gel route. Morphology, microstructure and electrochemical behavior of these cathode materials were evaluated. The resultant cathode material shows good electrochemical performance. Relatively low cost and simple preparation route make new xLi2MnO3˙(1-x)LiMn1/3Ni 1/3Co1/3O2 composite materials possible to use as potential cathode candidate for lithium-ion batteries.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical conductivity studies of graphene wrapped nanocrystalline LiMnPO{sub 4} composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheruku, Rajesh; D, Surya Bhaskaram; Govindaraj, G., E-mail: ggraj-7@yahoo.com

Nanocrystalline LiMnPO{sub 4} material was synthesized by template free sucrose assisted hydrothermal method. The material possesses the orthorhombic crystal structure with Pnma, space group having four formula units. The GO was prepared by the hummer’s method and it was reduced graphene oxide (rGO) with hydrazine hydrate in the presence of nitrogen atmosphere. LiMnPO{sub 4} material was wrapped by the rGO to increase its conductivity. The structural characterization was accomplished through X-ray diffraction, FT-IR and Raman spectroscopy. Morphology was identified by the SEM, Electrical characterization was done through impedance spectroscopy and the results were reported.

THE EFFECT OF SI DOPING ON THE ELECTROCHEMICAL CHARACTERISTICS OF LiNixMnyCo(1-x-y)O2

NASA Astrophysics Data System (ADS)

Na, Seong-Hwan; Kim, Hyun-Soo; Moon, Seong-In

A new simple way of synthesizing Li[NiMnCo]O2 was contrived and its electrochemical characteristics were enhanced by Si doping using solution-based synthetic route. The newly synthesized Li[NiMnCo]O2 showed capacity of 175mAh/g and good cycle life at as high cut-off voltage as 4.5V. Si-doping improved the rate capability, specific capacity, and cycle life of the material through increasing lattice parameters and lowering electrochemical impedance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Yuan; Wang, Junling, E-mail: jlwang@ntu.edu.sg; Zheng, Jianwei

Single n-type dopant in CuO has either a deep donor level or limited solubility, inefficient in generating free electrons. We have performed ab-initio study of the donor-acceptor codoping to obtain n-type CuO. Our results show that N codoping can slightly improve the donor level of Zr and In by forming shallower n-type complexes (Zr{sub Cu}-N{sub O} and 2In{sub Cu}-N{sub O}), but their formation energies are too high to be realized in experiments. However, Li codoping with Al and Ga is found to be relatively easy to achieve. 2Al{sub Cu}-Li{sub Cu} and 2Ga{sub Cu}-Li{sub Cu} have shallower donor levels than singlemore » Al and Ga by 0.14 eV and 0.08 eV, respectively, and their formation energies are reasonably low to act as efficient codopants. Moreover, Li codoping with both Al and Ga produce an empty impurity band just below the host conduction band minimum, which may reduce the donor ionization energy at high codoping concentrations.« less

TL and EPR studies of Cu, Ag and P doped Li2B4O7 phosphor

NASA Astrophysics Data System (ADS)

Can, N.; Karali, T.; Townsend, P. D.; Yildiz, F.

2006-05-01

Key characteristics of a newly prepared tissue-equivalent, highly sensitive thermoluminescence dosimeter, Li2B4O7:Cu,Ag,P, are presented. The material was developed at the Institute of Nuclear Sciences, Belgrade, in the form of sintered pellets. A new preparation procedure has greatly increased the sensitivity of the basic copper activated lithium borate and the glow curve of Li2B4O7 : Cu,Ag,P consists of a well-defined main dosimetric peak situated at about 460-465 K with a sensitivity which is about four to five times higher than that of LiF : Mg,Ti (TLD-100). The exceptionally good response features of Li2B4O7 : Cu,Ag,P are attributed to the incorporation of Cu as a dopant. Both low and high temperature emission spectra are presented and the origins of the various emission bands are considered. Additional data are provided from electron paramagnetic resonance measurements.

[Adsorption of Cu on Core-shell Structured Magnetic Particles: Relationship Between Adsorption Performance and Surface Properties].

PubMed

Li, Qiu-mei; Chen, Jing; Li, Hai-ning; Zhang, Xiao-lei; Zhang, Gao-sheng

2015-12-01

In order to reveal the relationship between the adsorption performance of adsorbents and their compositions, structure, and surface properties, the core-shell structured Fe₃O₄/MnO2 and Fe-Mn/Mn₂2 magnetic particles were systematically characterized using multiple techniques and their Cu adsorption behaviors as well as mechanism were also investigated in details. It was found that both Fe₃O4 and Fe-Mn had spinel structure and no obvious crystalline phase change was observed after coating with MnO₂. The introduction of Mn might improve the affinity between the core and the shell, and therefore enhanced the amount and distribution uniformity of the MnO₂ coated. Consequently, Fe-Mn/MnO₂ exhibited a higher BET specific surface area and a lower isoelectric point. The results of sorption experiments showed that Fe-Mn had a higher maximal Cu adsorption capacity of 33.7 mg · g⁻¹ at pH 5.5, compared with 17.5 mg · g⁻¹ of Fe₃O4. After coating, the maximal adsorption capacity of Fe-Mn/MnO₂ was increased to 58.2 mg · g⁻¹, which was 2.6 times as high as that of Fe₃O₄/MnO₂ and outperformed the majority of magnetic adsorbents reported in literature. In addition, a specific adsorption of Cu occurred at the surface of Fe₃O₄/MnO₂ or Fe-Mn/MnO₂ through the formation of inner-sphere complexes. In conclusion, the adsorption performance of the magnetic particles was positively related to their compositions, structure, and surface properties.

Dietary Manganese Modulates PCB126 Toxicity, Metal Status, and MnSOD in the Rat

PubMed Central

Wang, Bingxuan; Klaren, William D.; Wels, Brian R.; Simmons, Donald L.; Olivier, Alicia K.; Wang, Kai; Robertson, Larry W.; Ludewig, Gabriele

2016-01-01

PCB126 (3,3′,4,4′,5-pentachlorobiphenyl) is a potent aryl hydrocarbon receptor agonist and induces oxidative stress. Because liver manganese (Mn) levels decrease in response to PCB126, a Mn dietary study was designed to investigate the role of Mn in PCB126 toxicity. Male Sprague Dawley rats received diets containing 0, 10, or 150 ppm added Mn for 3 weeks, followed by a single ip injection of corn oil or PCB126 (5 µmol/kg body weight). After 2 weeks, Mn, Cu, Zn, and Fe levels in the heart, liver, and liver mitochondria, and Mn-containing superoxide dismutase (MnSOD) and metallothionein mRNA, MnSOD protein, and MnSOD activity were determined. Mn levels in liver, heart, and liver mitochondria were strongly decreased by the Mn-deficient diet. Small effects on Fe levels and a stepwise increase in MnSOD activity with dietary Mn were also visible. PCB126 caused profound changes in Cu (up), Zn, Fe, and Mn (down) in liver, but not in heart, and differing effects (Cu, Zn, and Fe up, Mn down) in liver mitochondria. Liver MnSOD and metallothionein mRNA levels and MnSOD protein were increased but MnSOD activity was decreased by PCB126. PCB126-induced liver enlargement was dose-dependently reduced with increasing dietary Mn. These changes in metals homeostasis and MnSOD activity in liver but not heart may be a/the mechanism of PCB126 liver-specific toxicity. Specifically, transport of Fenton metals (Cu, Fe) into and Mn out of the mitochondria, a probable mechanism for lower MnSOD activity, may be a/the cause of PCB126-induced oxidative stress. The role of metallothioneins needs further evaluation. Dietary Mn slightly alleviated PCB126-induced toxicities. PMID:26660635

Structure and Electrical Properties of Mn-Cu-O Spinels

NASA Astrophysics Data System (ADS)

Bobruk, M.; Durczak, K.; Dąbek, J.; Brylewski, T.

2017-04-01

The study presents the results of structural and electrical conductivity investigations of a Cu1.3Mn1.7O4 spinel obtained using EDTA gel processes. An amorphous gel was synthesized and calcinated for 5 h in air at temperatures of 673, 773, 873, and 973 K. When calcinating the gel at temperatures below 973 K, the obtained powders consisted of two phases—the regular Cu1.5Mn1.5O4 spinel and manganese(III) oxide. At 973 K, Mn2O3 was no longer observed, but a new Mn3O4 phase appeared in addition to the Cu1.5Mn1.5O4 spinel. Green bodies prepared from these powders were sintered for 2 h in air at 1393 K. The obtained sinters had a porosity of around 12% and were composed predominantly of the spinel phase, with minor amounts of Mn3O4 and, in the case of three of four sinters—CuO. Electrical conductivity measurements were taken over the temperature range of 300-1073 K. A change in the character of conductivity of the studied sinters was observed in the range of 400-430 K, and it was associated with an increase in activation energy from 0.20 to 0.56 eV. The electrical conductivity of the studied sinters ranged from 74.8 to 88.4 S cm-1, which makes the Cu1.3Mn1.7O4 material suitable for application as a protective-conducting coating in IT-SOFC ferritic stainless steel interconnects.

The effect of trace mineral source and concentration on ruminal digestion and mineral solubility.

PubMed

Genther, O N; Hansen, S L

2015-01-01

The objective of this experiment was to compare the effect of sources of sulfate trace mineral (STM) and hydroxy trace mineral (HTM) at different inclusions on digestibility of dry matter (DM) and neutral detergent fiber and solubility of Cu, Mn, and Zn in the rumen and abomasum of cattle. Five ruminally cannulated steers were used in a 5×5 Latin square design and individually fed a corn silage-based diet on an ad libitum basis. The 5 dietary treatments were as follows: control: no supplemental Cu, Mn, or Zn, analyzed to contain 7.4mg of Cu, 30.8mg of Mn, and 32.1mg of Zn per kilogram of diet DM (CON); low sulfate: 5mg of Cu/kg of DM supplemented from CuSO4, 15mg of Mn/kg of DM from MnSO4, and 30mg of Zn/kg of DM from ZnSO4; low HTM: 5mg of Cu/kg of DM supplemented from basic copper chloride (IntelliBond C; Micronutrients Inc., Indianapolis, IN), 15mg of Mn/kg of DM from manganese hydroxychloride (IntelliBond M; Micronutrients Inc.), and 30mg of Zn/kg of DM from zinc hydroxychloride (IntelliBond Z; Micronutrients Inc.); high sulfate: 25mg of Cu/kg of DM supplemented from CuSO4, 60mg of Mn/kg of DM from MnSO4, and 120mg of Zn/kg of DM from ZnSO4; and high HTM: 25mg of Cu/kg of DM supplemented from basic copper chloride, 60mg of Mn/kg of DM from manganese hydroxychloride, and 120mg of Zn/kg of DM from zinc hydroxychloride. Periods lasted for 12d, with 10d of diet adaptation. Dacron bags containing the CON total mixed ration were inserted on d 11 at 0h and were removed at 6, 12, 24, and 36h after insertion. Dry matter and neutral detergent fiber disappearances and rumen and simulated abomasal trace mineral solubilities were evaluated. Dietary treatment did not affect DM intake. Dry matter disappearance was lesser in supplemental TM treatments and greater in CON than the STM treatments, although the CON and HTM treatments did not differ. Neutral detergent fiber disappearance was not affected by treatment. Ruminally soluble Cu and Mn concentrations were least in CON and were lesser in HTM-containing treatments compared with STM treatments. However, in the abomasum, solubilities of Cu and Mn were similar across trace mineral sources. Ruminal and simulated abomasal soluble Zn was greater in the HTM treatments than in CON and STM, driven by the greater solubility of the high HTM treatment. Under the conditions of this study, supplementing trace minerals as STM decreased DM digestibility, whereas HTM did not affect DM digestibility. Additionally, Cu and Mn from HTM sources were relatively insoluble in the rumen but had similar solubility as STM at the pH found in the abomasum, suggesting that these minerals should be available for absorption in the intestine. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

PubMed

Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

2015-02-01

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties. Copyright © 2014. Published by Elsevier B.V.

Deep Eutectic Solvent Synthesis of LiMnPO4/C Nanorods as a Cathode Material for Lithium Ion Batteries

PubMed Central

Wu, Zhi; Huang, Rong-Rong; Yu, Hang; Xie, Yong-Chun; Lv, Xiao-Yan; Su, Jing; Long, Yun-Fei; Wen, Yan-Xuan

2017-01-01

Olivine-type LiMnPO4/C nanorods were successfully synthesized in a chloride/ethylene glycol-based deep eutectic solvent (DES) at 130 °C for 4 h under atmospheric pressure. As-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and electrochemical tests. The prepared LiMnPO4/C nanorods were coated with a thin carbon layer (approximately 3 nm thick) on the surface and had a length of 100–150 nm and a diameter of 40–55 nm. The prepared rod-like LiMnPO4/C delivered a discharge capacity of 128 mAh·g−1 with a capacity retention ratio of approximately 93% after 100 cycles at 1 C. Even at 5 C, it still had a discharge capacity of 106 mAh·g−1, thus exhibiting good rate performance and cycle stability. These results demonstrate that the chloride/ethylene glycol-based deep eutectic solvents (DES) can act as a new crystal-face inhibitor to adjust the oriented growth and morphology of LiMnPO4. Furthermore, deep eutectic solvents provide a new approach in which to control the size and morphology of the particles, which has a wide application in the synthesis of electrode materials with special morphology. PMID:28772493

Crystal Structure, Piezoelectric and Dielectric Properties of (Li, Ce)4+, Nb5+ and Mn2+ Co-doped CaBi4Ti4O15 High-Temperature Ceramics

NASA Astrophysics Data System (ADS)

Xin, Deqiong; Chen, Qiang; Wu, Jiagang; Bao, Shaoming; Zhang, Wen; Xiao, Dingquan; Zhu, Jianguo

2016-07-01

Bismuth-layered structured ceramics Ca0.85(Li,Ce)0.075Bi4Ti4- x Nb x O15-0.01MnCO3 were prepared by the conventional solid-state reaction method. The evolution of microstructure and corresponding electrical properties were studied. All the samples presented a single bismuth layered-structural phase with m = 4, indicating that (Li, Ce)4+, Nb5+ and Mn2+ adequately enter into the pseudo-perovskite structure and form solid solutions. It was found that Ca0.85(Li,Ce)0.075Bi4Ti3.98Nb0.02O15-0.01MnCO3 (CBTLCM-0.02Nb) ceramics possess the optimum electrical properties. The piezoelectric coefficient d 33, dielectric constant ɛ r, loss tan δ, planar electromechanical coupling factor k p and Curie-temperature T C of CBTLCM-0.02Nb ceramics were found to be ˜19.6 pC/N, 160, 0.16%, 8.1% and 767°C, respectively. Furthermore, the thermal depoling behavior demonstrates that the d 33 value of x = 0.02 content remains at 16.8 pC/N after annealing at 500°C. These results suggest that the (Li, Ce)4+-, Nb5+- and Mn2+-doped CBT-based ceramics are promising candidates for high-temperature piezoelectric applications.

Deep Eutectic Solvent Synthesis of LiMnPO₄/C Nanorods as a Cathode Material for Lithium Ion Batteries.

PubMed

Wu, Zhi; Huang, Rong-Rong; Yu, Hang; Xie, Yong-Chun; Lv, Xiao-Yan; Su, Jing; Long, Yun-Fei; Wen, Yan-Xuan

2017-02-06

Olivine-type LiMnPO₄/C nanorods were successfully synthesized in a chloride/ethylene glycol-based deep eutectic solvent (DES) at 130 °C for 4 h under atmospheric pressure. As-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and electrochemical tests. The prepared LiMnPO₄/C nanorods were coated with a thin carbon layer (approximately 3 nm thick) on the surface and had a length of 100-150 nm and a diameter of 40-55 nm. The prepared rod-like LiMnPO₄/C delivered a discharge capacity of 128 mAh·g -1 with a capacity retention ratio of approximately 93% after 100 cycles at 1 C. Even at 5 C, it still had a discharge capacity of 106 mAh·g -1 , thus exhibiting good rate performance and cycle stability. These results demonstrate that the chloride/ethylene glycol-based deep eutectic solvents (DES) can act as a new crystal-face inhibitor to adjust the oriented growth and morphology of LiMnPO₄. Furthermore, deep eutectic solvents provide a new approach in which to control the size and morphology of the particles, which has a wide application in the synthesis of electrode materials with special morphology.

Synthesis and electrochemical characterization of Li 1.05RE xCr yMn 2- x- yO 4 spinel as cathode material for rechargeable Li-battery

NASA Astrophysics Data System (ADS)

Xie, Yanting; Yang, Rudong; Yan, Lan; Qi, Lu; Dai, Kehua; He, Ping

The spinel phases of Li 1.05RE xCr yMn 2- x- yO 4 (RE = Sc, Ce, Pr, Tb; 0 ≤ x ≤ 0.05; 0 ≤ y ≤ 0.1) were prepared by a soft chemical method. The structural and electrochemical properties of Li 1.05RE xCr yMn 2- x- yO 4 were investigated by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and charge-discharge experiments. Rare earth element-Sc and transition metal-Cr as co-substituents stabilize the spinel framework and improve charge-discharge performance. For Li 1.05Sc 0.01Cr 0.03Mn 1.96O 4, the capacity of the cell maintained 95% of the initial capacity at the 80th cycle. The rare earth elements of the variable valent metals such as Ce 3+/4+, Pr 3+/4+, Tb 3+/4+ with transition metal Cr 3+ as co-substituent do not stable framework of spinel or improve the cycling performance. Cyclic voltammetry (CV) were measured to provide clues for the improved cycling performance of cathode electrodes.

NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as cathode material for high-performance lithium ion battery

NASA Astrophysics Data System (ADS)

Ye, Pan; Dong, Hui; Xu, Yunlong; Zhao, Chongjun; Liu, Dong

2018-01-01

Here we report a novel transitional metal oxide (NiCo2O4) coated Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as high-performance Li-ion battery cathode material. A thin layer of ∼10 nm NiCo2O4 was formed by simple wet-chemistry approach adjacent to the surface of Li[Ni0.03Mn1.97]O4 micro-/nano- spheres, leading to significantly enhanced battery electrochemical performance. The optimized sample(1 wt%) not only delivers excellent discharge capacity and cycling stability improvement at both room temperature and elevated temperatures, but also effectively prevents Mn dissolution while retaining its coating structure intact according to XRF and TEM results. The CV and EIS break-down analysis indicated a much faster electrochemical reaction kinetics, more reversible electrode process and greatly reduced charge transfer and Warburg resistance, clearly illustrating the dual role of NiCo2O4 coating to boost electron transport and Li+ diffusion, and alleviation of manganese dissolving. This approach may render as an efficient technique to realize high-performance lithium ion battery cathode material.

Evaluation of the microstructure of Al-Cu-Li-Ag-Mg Weldalite (tm) alloys, part 4

NASA Technical Reports Server (NTRS)

Pickens, Joseph R.; Kumar, K. S.; Brown, S. A.; Gayle, Frank W.

1991-01-01

Weldalite (trademark) 049 is an Al-Cu-Li-Ag-Mg alloy designed to have ultrahigh strength and to serve in aerospace applications. The alloy displays significantly higher strength than competitive alloys in both naturally aged and artificially aged tempers. The strengthening phases in such tempers have been identified to, in part, explain the mechanical properties attained. In general, the alloy is strengthened by delta prime Al3Li and Guinier-Preston (GP) zones in the naturally aged tempers. In artificially aged tempers in slightly underaged conditions, strengthening is provided by several phases including GP zones, theta prime Al2Cu, S prime Al2CuMg, T(sub 1) Al2CuLi, and possibly a new phase. In the peak strength artificially aged tempers, T(sub 1) is the predominant strengthening phase.

Concentration dependence of Li+/Na+ diffusion in manganese hexacyanoferrates

NASA Astrophysics Data System (ADS)

Takachi, Masamitsu; Fukuzumi, Yuya; Moritomo, Yutaka

2016-06-01

Manganese hexacyanoferrates (Mn-HCFs) with a jungle-gym-type structure are promising cathode materials for Li+/Na+ secondary batteries (LIBs/SIBs). Here, we investigated the diffusion constants D Li/D Na of Li+/Na+ against the Li+/Na+ concentration x Na/x Li and temperature (T) of A 1.32Mn[Fe(CN)6]0.833.6H2O (A = Li and Na). We evaluated the activation energy E\\text{a}\\text{Li}/E\\text{a}\\text{Na} of D Li/D Na against x Na/x Li. We found that E\\text{a}\\text{Na} steeply increases with x Na from 0.41 eV at x Na = 0.69 to 0.7 eV at 1.1. The increase in E\\text{a}\\text{Na} is ascribed to the occupancy effect of the Na+ site. The increase in E\\text{a}\\text{Li} is suppressed, probably because the number of Li+ sites is three times that of Na+ sites.

Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas.

PubMed

Tanaka, Manabu; Kageyama, Takuya; Sone, Hirotaka; Yoshida, Shuhei; Okamoto, Daisuke; Watanabe, Takayuki

2016-04-06

Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems-Li-Mn, Li-Cr, Li-Co, and Li-Ni-were compared to understand formation mechanism of Li-Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li-Me oxide nanoparticles were successfully synthesized in Li-Mn, Li-Cr, and Li-Co systems. Spinel structured LiMn₂O₄ with truncated octahedral shape was formed. Layer structured LiCrO₂ or LiCoO₂ nanoparticles with polyhedral shapes were also synthesized in Li-Cr or Li-Co systems. By contrast, Li-Ni oxide nanoparticles were not synthesized in the Li-Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles.

Secondary battery material and synthesis method

DOEpatents

Liu, Hongjian; Kepler, Keith Douglas; Wang, Yu

2013-10-22

A composite Li.sub.1+xMn.sub.2-x-yM.sub.yO.sub.4 cathode material stabilized by treatment with a second transition metal oxide phase that is highly suitable for use in high power and energy density Li-ion cells and batteries. A method for treating a Li.sub.1+xMn.sub.2-x-yM.sub.yO.sub.4 cathode material utilizing a dry mixing and firing process.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

PubMed

Lorenz, Volker; Ehle, Sophie; Liebing, Phil; Engelhardt, Felix; Hashemi-Haeri, Haleh; Oehler, Florian; Hinderberger, Dariush; Busse, Sabine; Urbaschok, Jens; Edelmann, Frank T

2017-12-19

A unique trivalent manganese siloxide complex, blue-violet Mn III Li 2 Cl[(Ph 2 SiO) 2 O] 2 (THF) 4 ·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph 2 SiOH) 2 O (1) followed by reaction with MnCl 2 (THF) 2 gave the structurally remarkable Mn(ii) precursor Mn II Li 4 Cl 2 [(Ph 2 SiO) 2 O] 2 (THF) 5 ·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO 4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

Inorganic Macro- and Micronutrients in "Superberries" Black Chokeberries (Aronia melanocarpa) and Related Teas.

PubMed

Juranović Cindrić, Iva; Zeiner, Michaela; Mihajlov-Konanov, Darija; Stingeder, Gerhard

2017-05-18

Black chokeberries ( Aronia melanocarpa ) are considered to be functional food containing high amounts of anthocyanins, phenols, antioxidants, vitamins and minerals. Whereas organic compounds are well studied, there is little research on the mineral composition of the chokeberries. Thus, the presented study is focused on the determination of Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Se, Sr and Zn in black chokeberry fruits and infusions to study the metals' extractability. The nutrients Ca, K and Mg are present in the fruits (dried matter) at g/kg level, whereas the other elements are present from µg/kg up to mg/kg level. The extraction yields of the metals from the infusion range from 4 (Al, Mn) up to 44% (Na). The toxic elements present do not pose any health risk when berries or infusions are consumed. Concluding, Aronia berries, as well as infusions derived from them, are a good dietary source of essential metals in addition to the organic compounds also contained.

Dynamic study of (De)sodiation in alpha-MnO 2 nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Yifei; Ma, Lu; He, Kun

2016-01-01

In this report, the electrochemical sodiation and desodiation in single crystalline alpha-MnO 2 nanowires are studied dynamically at both single particle level using in situ transmission electron microscopy (TEM) and bulk level using in situ synchrotron X-ray. The TEM results suggest that the first sodiation process starts with tunnel-based Na + intercalation, experiences the formation of Na 0.5MnO 2 as a result of tunnel degradation, and ends with the Mn 2O 3 phase. The inserted Na + can be partially extracted out of the sodiated products, and the following cycles are dominated by the reversible conversion reaction between Na 0.5MnOmore » 2 and Mn 2O 3. The Mn valence evolution inside a cycling coin using alpha-MnO 2 nanowire electrode also exhibits partially reversible characteristic, agreeing well with the in situ TEM analysis. The sodiation is compared with lithiation in the same alpha-MnO 2 nanowires. Both Na + and Li + interact with the tunneled structure via a similar tunnel -driven intercalation mechanism before Mn 4+ is reduced to Mn 3.5+. For the following deep insertion, the tunnels survive up. to LiMnO 2 (Mn3+) during lithiation, while the sodiation proceeds via a different mechanism that involves obvious phase transition and fast tunnel degradation after Mn's valence is below 3.5+. The difference in charge carrier insertion mechanisms can be ascribed to the strong interaction between the tunnel frame and inserted Na + possessing a larger ionic size than inserted Li +.« less

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Geochemical landscapes of the conterminous United States; new map presentations for 22 elements

USGS Publications Warehouse

Gustavsson, N.; Bolviken, B.; Smith, D.B.; Severson, R.C.

2001-01-01

Geochemical maps of the conterminous United States have been prepared for seven major elements (Al, Ca, Fe, K, Mg, Na, and Ti) and 15 trace elements (As, Ba, Cr, Cu, Hg, Li, Mn, Ni, Pb, Se, Sr, V, Y, Zn, and Zr). The maps are based on an ultra low-density geochemical survey consisting of 1,323 samples of soils and other surficial materials collected from approximately 1960-1975. The data were published by Boerngen and Shacklette (1981) and black-and-white point-symbol geochemical maps were published by Shacklette and Boerngen (1984). The data have been reprocessed using weighted-median and Bootstrap procedures for interpolation and smoothing.

Thermally stimulated luminescence studies of undoped, Cu- and Mn-doped CaSO4 compounds

NASA Astrophysics Data System (ADS)

Manam, J.; Das, S.

Thermally stimulated luminescence (TSL) of undoped and doped CaSO4 with activators such as Cu and Mn has been investigated. The polycrystalline samples of undoped and doped CaSO4 are prepared by the melting method. The formation of CaSO4 compound is confirmed by X-ray diffraction and Fourier transform infrared studies. Scanning electron microscopic studies of CaSO4 are also carried out. The TSL glow curves of undoped CaSO4, Cu- and Mn-doped CaSO4 are studied. Comparison of the thermoluminescence (TL) intensity of the most intensive glow peak of Cu-doped CaSO4 compound with that of undoped CaSO4 shows that addition of Cu impurity in CaSO4 compound enhances the TL intensity by about four times. However, the addition of Mn impurity to undoped CaSO4 increases the TL intensity by about three times when compared with that of undoped CaSO4. The TL-dose dependence of all three samples was studied and was observed to be almost linear in the studied range of irradiation time. Among the samples studied, namely undoped CaSO4 and Cu- and Mn-doped CaSO4, Cu-doped CaSO4 is found to be the most sensitive. The trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peaks of CaSO4:Mn, CaSO4:Cu and CaSO4 phosphors were determined using the glow curve shape (Chen's) method.

Characterization of Electronic and Ionic Transport in Li 1- xNi 0.33Mn 0.33Co 0.33O 2 (NMC 333) and Li 1- xNi 0.50Mn 0.20Co 0.30O 2 (NMC 523) as a Function of Li Content

DOE PAGES

Amin, Ruhul; Chiang, Yet -Ming

2016-05-13

Despite the extensive commercial use of Li 1-xNi 1-y-zMn zCo yO 2 (NMC) as the positive electrode in Li-ion batteries, and its long research history, its fundamental transport properties are poorly understood. These properties are crucial for designing high energy density and high power Li-ion batteries. Here, the transport properties of NMC 333 and NMC 523 are investigated using impedance spectroscopy and DC polarization and depolarization techniques. The electronic conductivity is found to increase with decreasing Li-content (increasing state-of-charge) from ~10 –7 Scm –1 to ~10 –2 Scm –1 over Li concentrations x = 0.00 to 0.75, corresponding to anmore » upper charge voltage of 4.8 V with respect to Li/Li +. The lithium ion diffusivity is at least one order of magnitude lower, and decreases with increasing x to at x = ~0.5. As a result, the ionic conductivity and diffusivity obtained from the two measurements techniques (EIS and DC) are in good agreement, and chemical diffusion is limited by lithium transport over a wide state-of-charge range.« less

Synthesis of LaMnO3 in molten chlorides: effect of preparation conditions.

PubMed

Vradman, Leonid; Zana, Jonatan; Kirschner, Alon; Herskowitz, Moti

2013-07-14

LaMnO3 perovskite was successfully synthesized in molten chlorides. In order to explore the effect of the molten salt type, NaCl-KCl and LiCl-KCl eutectic mixtures were employed as a liquid medium for the perovskite formation process. The synthesis included heating the La-nitrate, Mn-nitrate and chlorides mixture to above the melting point of the corresponding chlorides. This procedure yielded a LaMnO3 phase integrated in the fused chloride matrix. Washing with water removed the salts completely, yielding pure LaMnO3 perovskite crystals. The synthesis without molten salt at 800 °C yielded several by-products in addition to the LaMnO3 phase, while with LiCl-KCl the pure perovskite phase was obtained at temperatures as low as 600 °C. Variation of temperature in the range 600-800 °C for LiCl-KCl and 700-800 °C for NaCl-KCl had no significant effect either on the morphology or on the particle size of the product. On the other hand, the effect of the molten salt type on the morphology and size of perovskite particles was remarkable. The synthesis in NaCl-KCl resulted in sub-micron LaMnO3 particles with shapes that range from truncated hexahedrons to spheres, while in LiCl-KCl mostly cubic particles of up to 2-microns were obtained. The effect of the molten salt type on LaMnO3 perovskite formation is explained based on the nucleation and crystal growth model and difference in the melting point of eutectic mixtures.

Metallic ions catalysis for improving bioleaching yield of Zn and Mn from spent Zn-Mn batteries at high pulp density of 10.

PubMed

Niu, Zhirui; Huang, Qifei; Wang, Jia; Yang, Yiran; Xin, Baoping; Chen, Shi

2015-11-15

Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu(2+) improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu(2+) content increased from 0 to 0.8 g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu(2+) catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe(3+) based on a cycle of Fe(3+)/Fe(2+). However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe(3+)/Fe(2+), stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu(2+) catalytic bioleaching of spent ZMBs. Copyright © 2015 Elsevier B.V. All rights reserved.

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials.

PubMed

Ma, Ya; Cui, Yan; Zuo, Xiaoxi; Huang, Shanna; Hu, Keshui; Xiao, Xin; Nan, Junmin

2014-10-01

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn-Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H2SO4 (2 mol L(-1)) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37-40°C and 300 A m(-2). The most of MnO2 and a small quantity of electrolytic MnO2 are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi0.5Mn1.5O4 material of lithium-ion battery. The as-synthesized LiNi0.5Mn1.5O4 discharges 118.3 mAh g(-1) capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO2. This process can recover the substances in the spent Zn-Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable. Copyright © 2014 Elsevier Ltd. All rights reserved.

Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

DOE PAGES

Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.; ...

2014-09-30

Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li 1.2Mn 0.55Ni 0.15Co 0.1O 2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxidemore » occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(Li Lioct →Li Litet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [Li TM oct → Li Litet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [Mn TMoct Mn Litet Mn Lioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.« less

Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jianming; Xu, Pinghong; Gu, Meng

2015-02-24

Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defectmore » spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.« less

Cu+ association to some Ph-X (X = OH, NH2, CHO, COOH, CF3) phenyl derivatives.: A comparison with Li+ complexes

NASA Astrophysics Data System (ADS)

Corral, Ines; Mo, Otilia; Yanez, Manuel

2006-09-01

The complexes of Cu+ with phenol, aniline, benzaldehyde, benzoic acid, and trifluromethyl-benzene were investigated through the use of MP2 and density functional theory (DFT) methods. Both harmonic vibrational frequencies and optimized geometries were obtained at the B3LYP/6-311G(d,p) and MP2(full)/6-311G(d,p) levels of theory. Final energies were obtained through single point B3LYP/6-311+G(3df,2p)//B3LYP/6-311G(d,p) calculations. The interactions of Cu+ with these aromatic compounds have a non-negligible covalent character, which clearly differentiate Cu+-complexes from the corresponding Li+-complexes. These dissimilarities are reflected in the geometries, binding energies and infrared spectra of the most stable adducts. For Li+ only conventional [pi]-complexes should be expected when interacting with aniline, while Cu+ attaches preferentially to the para carbon atom. For phenol, besides the conventional [pi]-complexes, a 12% of oxygen attached species are expected to be found upon Li+ association. Conversely, no oxygen attached species should be formed in reactions of phenol with Cu+. For benzoic acid and benzaldehyde, Li+ aligns with the dipole moment of the base, interacting exclusively with the carbonyl oxygen in the plane of the molecule. This is also the case in Cu+-benzoic acid complex, while in the Cu+-benzaldehyde complex the metal ion also interacts with the aromatic [pi]-system. Cu+ binding enthalpies (BEs) are systematically larger (about 1.3 times) than Li+ BEs. The covalent character of Cu+ interactions is associated with electron donations from bonding ([pi]) orbitals or lone-pairs of the base toward the 4s empty orbital of the metal and with back-donations from the occupied d orbitals of the metal toward antibonding ([pi]*) empty orbitals of the base. This non-negligible covalent character is also reflected in a rough correlation between the calculated Cu+ BEs and the available experimental proton affinities that does not exist for Li+ BEs.

High-resolution structural studies of ultra-thin magnetic, transition metal overlayers and two-dimensional transition metal oxides using synchrotron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kellar, S.A.

This thesis report the surface-structure determination of three, ultra-thin magnetic transition-metal films, Fe/Au(100), Mn/Ni(100), and Mn/Cu(100) using Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) and photoelectron holography. These structural studies are the first to use non-s initial states in the ARPEFS procedure. This thesis also reports an ARPEFS surface-structure determination of a two-dimensional transition-metal oxide, [(1 x 1)O/W(110)] x 12. The authors have analyzed the ARPFES signal from the Au 4f{sub 7/5} core level of the Au(1 ML)/Fe(15 ML)/Au(100) system. The analysis shows that the Fe grows layer by layer with one monolayer of gold, acting as a surfactant, remaining onmore » top of the growing Fe layers. These surface gold atoms sit in the four-fold hollow site, 1.67 {+-} 0.02 A above the iron surface. The grown Fe layer is very much like the bulk, bcc iron, with an interlayer spacing of 1.43 {+-} 0.03 A. Analysis of the Mn 3p ARPEFS signals from c(2 x 2)Mn/Ni(100) and c(2 x 2)Mn/Cu(100) shows that the Mn forms highly corrugated surface alloys. The corrugation of the Mn/Ni(100) and Mn/Cu(100) systems are 0.24 {+-} 0.02 A and 0.30 {+-} 0.04 A respectively. In both cases the Mn is sticking above the plane of the surface substrate atoms. For the Mn/Ni(100) system the first layer Ni is contracted 4% from the bulk value. The Mn/Cu(100) system shows bulk spacing for the substrate Cu. Photoelectron holography shows that the Mn/Ni interface is very abrupt with very little Mn leaking into the second layer, while the Mn/Cu(100) case has a significant amount of Mn leaking into the second layer. A new, five-element electrostatic electron lens was developed for hemispherical electron-energy analyzers. This lens system can be operated at constant transverse or constants angular magnification, and has been optimized for use with the very small photon-spot sizes. Improvements to the hemispherical electron-energy analyzer are also discussed.« less

In Situ Encapsulating α-MnS into N,S-Codoped Nanotube-Like Carbon as Advanced Anode Material: α → β Phase Transition Promoted Cycling Stability and Superior Li/Na-Storage Performance in Half/Full Cells.

PubMed

Liu, Dai-Huo; Li, Wen-Hao; Zheng, Yan-Ping; Cui, Zheng; Yan, Xin; Liu, Dao-Sheng; Wang, Jiawei; Zhang, Yu; Lü, Hong-Yan; Bai, Feng-Yang; Guo, Jin-Zhi; Wu, Xing-Long

2018-04-02

Incorporation of N,S-codoped nanotube-like carbon (N,S-NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α-MnS nanoparticles (NPs) are in situ encapsulated into N,S-NTC, preparing an advanced anode material (α-MnS@N,S-NTC) for lithium-ion/sodium-ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li-storage properties, which is deduced by the studies of ex situ X-ray diffraction/high-resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α-MnS@N,S-NTC electrode delivers a high Li-storage capacity (1415 mA h g -1 at 50 mA g -1 ), excellent rate capability (430 mA h g -1 at 10 A g -1 ), and long-term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g -1 ) with retained morphology. In addition, the N,S-NTC-based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α-MnS@N,S-NTC also delivers high Na-storage capacity (536 mA h g -1 at 50 mA g -1 ) without the occurrence of such α → β phase transition and excellent full-cell performances as coupling with commercial LiFePO 4 and LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathodes in LIBs as well as Na 3 V 2 (PO 4 ) 2 O 2 F cathode in SIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping Structure-Composition-Property Relationships in V- and Fe-Doped LiMnPO4 Cathodes for Lithium-Ion Batteries.

PubMed

Johnson, Ian D; Loveridge, Melanie; Bhagat, Rohit; Darr, Jawwad A

2016-11-14

A series of LiMn 1-x-y Fe x V y PO 4 (LMFVP) nanomaterials have been synthesized using a pilot-scale continuous hydrothermal synthesis process (CHFS) and evaluated as high voltage cathodes in Li-ion batteries at a production rate of 0.25 kg h -1 . The rapid synthesis and screening approach has allowed the specific capacity of the high Mn content olivines to be optimized, particularly at high discharge rates. Consistent and gradual changes in the structure and performance are observed across the compositional region under investigation; the doping of Fe at 20 at% (with respect to Mn) into lithium manganese phosphate, rather than V or indeed codoping of Fe and V, gives the best balance of high capacity and high rate performance.

Synthesis and Electrochemical Property of LiMn2O4 Porous Hollow Nanofiber as Cathode for Lithium-Ion Batteries.

PubMed

Duan, Lianfeng; Zhang, Xueyu; Yue, Kaiqiang; Wu, Yue; Zhuang, Jian; Lü, Wei

2017-12-01

The LiMn 2 O 4 hollow nanofibers with a porous structure have been synthesized by modified electrospinning techniques and subsequent thermal treatment. The precursors were electrospun directly onto the fluorine-doped tin oxide (FTO) glass. The heating rate and FTO as substrate play key roles on preparing porous hollow nanofiber. As cathode materials for lithium-ion batteries (LIBs), LiMn 2 O 4 hollow nanofibers showed the high specific capacity of 125.9 mAh/g at 0.1 C and a stable cycling performance, 105.2 mAh/g after 400 cycles. This unique structure could relieve the structure expansion effectively and provide more reaction sites as well as shorten the diffusion path for Li + for improving electrochemical performance for LIBs.

In Situ Chelating Synthesis of Hierarchical LiNi1/3 Co1/3 Mn1/3 O2 Polyhedron Assemblies with Ultralong Cycle Life for Li-Ion Batteries.

PubMed

Zhang, Yue; Jia, Dianzeng; Tang, Yakun; Huang, Yudai; Pang, Weikong; Guo, Zaiping; Zhou, Zhen

2018-06-03

Layered lithium transition-metal oxides, with large capacity and high discharge platform, are promising cathode materials for Li-ion batteries. However, their high-rate cycling stability still remains a large challenge. Herein, hierarchical LiNi 1/3 Co 1/3 Mn 1/3 O 2 polyhedron assemblies are obtained through in situ chelation of transition metal ions (Ni 2+ , Co 2+ , and Mn 2+ ) with amide groups uniformly distributed along the backbone of modified polyacrylonitrile chains to achieve intimate mixing at the atomic level. The assemblies exhibit outstanding electrochemical performances: superior rate capability, high volumetric energy density, and especially ultralong high-rate cyclability, due to the superiority of unique hierarchical structures. The polyhedrons with exposed active crystal facets provide more channels for Li + diffusion, and meso/macropores serve as access shortcuts for fast migration of electrolytes, Li + and electrons. The strategy proposed in this work can be extended to fabricate other mixed transition metal-based materials for advanced batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemistry and safety of Li 4Ti 5O 12 and graphite anodes paired with LiMn 2O 4 for hybrid electric vehicle Li-ion battery applications

NASA Astrophysics Data System (ADS)

Belharouak, Ilias; Koenig, Gary M.; Amine, K.

A promising anode material for hybrid electric vehicles (HEVs) is Li 4Ti 5O 12 (LTO). LTO intercalates lithium at a voltage of ∼1.5 V relative to lithium metal, and thus this material has a lower energy compared to a graphite anode for a given cathode material. However, LTO has promising safety and cycle life characteristics relative to graphite anodes. Herein, we describe electrochemical and safety characterizations of LTO and graphite anodes paired with LiMn 2O 4 cathodes in pouch cells. The LTO anode outperformed graphite with regards to capacity retention on extended cycling, pulsing impedance, and calendar life and was found to be more stable to thermal abuse from analysis of gases generated at elevated temperatures and calorimetric data. The safety, calendar life, and pulsing performance of LTO make it an attractive alternative to graphite for high power automotive applications, in particular when paired with LiMn 2O 4 cathode materials.

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

PubMed

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

Tuning the Morphologies of MnO/C Hybrids by Space Constraint Assembly of Mn-MOFs for High Performance Li Ion Batteries.

PubMed

Sun, Dan; Tang, Yougen; Ye, Delai; Yan, Jun; Zhou, Haoshen; Wang, Haiyan

2017-02-15

Morphology controllable fabrication of electrode materials is of great significance but is still a major challenge for constructing advanced Li ion batteries. Herein, we propose a novel space constraint assembly approach to tune the morphology of Mn(terephthalic acid) (PTA)-MOF, in which benzonic acid was employed as a modulator to adjust the available MOF assembly directions. As a result, Mn(PTA)-MOFs with microquadrangulars, microflakes, and spindle-like microrods morphologies have been achieved. MnO/C hybrids with preserved morphologies were further obtained by self-sacrificial and thermal transformation of Mn(PTA)-MOFs. As anodes for Li ion batteries, these morphologies showed great influence on the electrochemical properties. Owing to the abundant porous structure and unique architecture, the MnO/C spindle-like microrods demonstrated superior electrochemical properties with a high reversible capacity of 1165 mAh g -1 at 0.3 A g -1 , excellent rate capability of 580 mAh g -1 at 3 A g -1 , and no considerable capacity loss after 200 cycles at 1 A g -1 . This strategy could be extended to engineering the morphology of other MOF-derived functional materials in various structure-dependent applications.

Recent advances on Fe- and Mn-based cathode materials for lithium and sodium ion batteries

NASA Astrophysics Data System (ADS)

Zhu, Xiaobo; Lin, Tongen; Manning, Eric; Zhang, Yuancheng; Yu, Mengmeng; Zuo, Bin; Wang, Lianzhou

2018-06-01

The ever-growing market of electrochemical energy storage impels the advances on cost-effective and environmentally friendly battery chemistries. Lithium-ion batteries (LIBs) are currently the most critical energy storage devices for a variety of applications, while sodium-ion batteries (SIBs) are expected to complement LIBs in large-scale applications. In respect to their constituent components, the cathode part is the most significant sector regarding weight fraction and cost. Therefore, the development of cathode materials based on Earth's abundant elements (Fe and Mn) largely determines the prospects of the batteries. Herein, we offer a comprehensive review of the up-to-date advances on Fe- and Mn-based cathode materials for LIBs and SIBs, highlighting some promising candidates, such as Li- and Mn-rich layered oxides, LiNi0.5Mn1.5O4, LiFe1-xMnxPO4, NaxFeyMn1-yO2, Na4MnFe2(PO4)(P2O7), and Prussian blue analogs. Also, challenges and prospects are discussed to direct the possible development of cost-effective and high-performance cathode materials for future rechargeable batteries.

Structure and Differentiated Electrical Characteristics of M1/2La1/2Cu3Ti4O12 (M = Li, Na, K) Ceramics Prepared by Sol-Gel Method

NASA Astrophysics Data System (ADS)

Liu, Zhanqing; Yang, Zupei

2017-10-01

New M1/2La1/2Cu3Ti4O12 (M = Li, Na, K) ceramics based on partial substitution of Li+, Na+, and K+ for La3+ in La2/3Cu3Ti4O12 (LCTO) have been prepared by a sol-gel method, and the effects of Li+, Na+, and K+ on the microstructure and electrical properties investigated in detail, revealing different results depending on the substituent. The cell parameter increased with increasing radius of the substituent ion (Li+, Na+, K+). Li1/2La1/2Cu3Ti4O12 (LLCTO) ceramic showed better frequency and temperature stability, but the dielectric constant decreased and the third abnormal dielectric peak disappeared from the dielectric temperature spectrum. Na1/2La1/2Cu3Ti4O12 (NLCTO) ceramic exhibited higher dielectric constant and better frequency and temperature stability, and displayed the second dielectric relaxation in electric modulus plots. The performance of K1/2La1/2Cu3Ti4O12 (KLCTO) ceramic was deteriorated. These different microstructures and electrical properties may be due to the effect of different defect structures generated in the ceramic as well as grain size. This work represents the first analysis and comparison of these remarkable differences in the electrical behavior of ceramics obtained by partial substitution of Li+, Na+, and K+ for La3+ in LCTO.

Investigation of the mineralogy and the sorption mechanism of Ni, Cu, Co and Mo by turbostratic phyllomanganates of Mn-nodules from the eastern equatorial Pacific Ocean using XAS

NASA Astrophysics Data System (ADS)

Wegorzewski, A.; Webb, S.; Grangeon, S.; Kuhn, T.

2016-12-01

Mn-nodules are Mn-Fe (oxy)hydroxides bearing high amounts of economically important metals such as Ni, Cu, Co, Mo, as well as high field strength elements. According to that nodules are interesting for science and industry. Especially the sorption sites of metals (Ni, Cu, Mo) by the mineral phases are important to understand their coordination environment and further to tailor a specific metallurgical treatment in order to optimize the metal extraction procedure. Nodules used for this study were sampled from the German license area within the Clarion Clipperton Zone in the Pacific. These nodules grow on the seafloor in 4200 m depth by metal precipitation from oxic (hydrogenetic growth) and/or suboxic waters (suboxic diagenetic growth; Halbach et al., 1988). They show a complex texture characterized by irregular, concentrically banded nm- to µm-thick layered growth structures (LGS). Electronmicroprobe and X-ray diffraction analyses reveal: suboxic diagenetic LGS have high Mn/Fe ratios (9-826; Mn ≈ 40 wt. %; Fe ≈ 0.5 wt %), high Ni (0.3-2.6 wt %) and Cu (0.5-3.0 wt %) contents but low Co content (0.02±0.01 wt %). Mineralogically those LGS are turbostratic phyllomanganates (vernadite), which consist of [MnO6]-octahedral layers, separated from each other by cations (e.g., Na, Mg) and water in the interlayer, forming 7 and 10 Å phyllomanganates (Bode et al., 2007). In contrast hydrogenetic LGS show low Mn/Fe ratios (<5), low Ni+Cu content (<1 wt%) but enrichment in Co (≤0.5 wt%). Those LGS are of δ-MnO2, which is epitaxially intergrown with an amorphous FeOOH phase. In general, phyllomanganates have a high opportunity to incorporate metals due to their negative layer charge deficit cause by abundant isomorphic substitution of Mn4+ by Mn3+ and vacancies within MnO2 sheets. The negative charge deficit can be balanced by hydrated interlayer cations (e.g., Na, Mg) or due to metals adsorption at cation vacancy sites, incorporation into the MnO2 sheet and/or adsorption at lateral edge surfaces (Peacock, 2009; Pena et al., 2015). A special emphasis of this study was to determine the boundings of Ni, Cu, Co and Mo by the Mn-mineral phases of nodules. X-ray absorption spectroscopy analyses show that metals such as Ni, Cu, Co are rather incorporated into MnO2 sheets than adsorbed as inner-sphere complexes over/below vacancies, like Mo.

Synthesis and Performance of LiFe1-xMnxPO4 in Lithium-ion Battery

NASA Astrophysics Data System (ADS)

Bazzi, Khadije; Nazri, Maryam; Vaishnava, Prem; Naik, Vaman; Nazri, Gholam-Abbas; Naik, Ratna

2013-03-01

Olivine-type lithium transition metal phosphates (i.e. LiFePO4) have been intensively investigated as promising electrode materials for rechargeable lithium-ion batteries. There have been attempts to improve energy density and voltage quality of phosphate based electrode. In this study, we have partially substituted FeII/FeIII redox center with MnII/MnIII in LiFePO4 that provides over 600 mV higher voltage. We prepared various compositions of LiFe1-xMnxPO4 (x =0, 0.2, 0.4, 0.6, 0.8 and 1) between the two end members (LiFePO4 - LiMnPO4) . Due to intrinsic low electronic conductivity of lithium transition metal phosphates, we coat these materials with a uniform conductive carbon through a unique sol-gel process developed in our laboratory. In addition, we made a composite of the carbon coated phosphate with carbon nano-tubes to develop a highly conductive matrix electrode. We report the materials structure, morphology, electrical conductivity and electrochemical performances of LiFe1-xMnxPO4 using XRD, Raman spectroscopy, SEM, TEM, XPS, electrical conductivity and galvanostatic charge/discharge measurements.

Electrochemical Performance of LiNi0.5Mn1.5O4 by Sol-gel Self-combustion Reaction Method in Different Kinds of Electrolyte for High-voltage Rechargeable Lithium Cells

NASA Astrophysics Data System (ADS)

Liang, Xinghua; Shi, Lin; Liu, Yusi; Zeng, Shuaibo; Ye, Chaochao

2015-07-01

LiNi0.5Mn1.5O4 cathode material was synthesized through sol-gel self-combustion reaction method. LiNi0.5Mn1.5O4 powders were subsequently characterized as cathode materials in a Li-ion coin cell comprising a Li anode with electrolyte A or electrolyte B. 1.0 mol/L Lithium Hexafluorophosphate (LiPF6) dissolved in volume ration of ethylene carbonate (EC) to ethyl methyl carbonate (EMC) to diethyl carbonate (DEC) corresponded to 4:3:3as electrolyte A, 1.0 mol/L LiPF6 dissolved in volume ration of EC to EMC to DEC corresponded to 4:2:4 as electrolyte B. Electrochemical performance of lithium cells was evaluated. These tests showed that no matter the cells with electrolyte A or electrolyte B has good discharge platform in 4.7V range (3.5V-4.75V) at the rate of 0.1C, the initial discharge capacity of cell with electrolyte B was higher than that with electrolyte A.

Analysis of the Metals in Soil-Water Interface in a Manganese Mine

PubMed Central

Ren, Bozhi; Wang, Qian; Chen, Yangbo; Ding, Wenjie; Zheng, Xie

2015-01-01

In order to reveal the influence of the metals of soil-water interface in a manganese mine (Xiangtan, China), on local water environment, there are six kinds of metals (Mn, Ni, Cu, Zn, Cd, and Pb) characterized by measuring their concentration, correlation, source, and special distribution using principal component analysis, single factor, and Nemero comprehensive pollution index. The results showed that the corresponding average concentration was 0.3358, 0.045, 0.0105, 0.0148, 0.0067, and 0.0389 mg/L. The logarithmic concentration of Mn, Zn, and Pb was normal distribution. The correlation coefficients (between Mn and Pb, Mn and Zn, Mn and Ni, Cu and Zn, Cu and Pb, and Zn and Cd) were found to range from 0.5 to 0.6, and those between Cu and Ni and Cu and Cd were below 0.3. It was found that Zn and Mn pollution were caused primarily by ore mining, mineral waste transportation, tailing slag, and smelting plants, while Cu and Ni mainly originate from the mining industry activities and the traffic transportation in the mining area. In addition, the Cd was considered to be produced primarily from the agricultural or anthropogenic activities. The pollution indexes indicated that metal pollution degree was different in soil-water interface streams as listed in increasing order of pollution level as Zn > Ni > Cu > Pb > Mn > Cd. For all of the pollution of the soil-water interface streams, there was moderate metal pollution but along the eastern mine area the pollution seemed to get more serious. There was only a small amount of soil-water interface streams not contaminated by the metals. PMID:26167333

[Spatial variability and evaluation of soil heavy metal contamination in the urban-transect of Shanghai].

PubMed

Liu, Yun-Long; Zhang, Li-Jia; Han, Xiao-Fei; Zhuang, Teng-Fei; Shi, Zhen-Xiang; Lu, Xiao-Zhe

2012-02-01

Soil heavy metal concentrations along the typical urban-transect in Shanghai were analyzed to indicate the effect of urbanization and industrialization on soil environment quality. Spatial variation structure and distribution of 5 heavy metals (Cu, Cr, Mn, Pb and Zn) in the top soil of urban-transect were analyzed. The single pollution index and the composite pollution index were used to evaluate the soil heavy metal pollution. The results showed that the average concentrations of the Cu, Pb, Zn, Cr, Mn were 27.80, 28.86, 99.36, 87.72, 556.97 mg x kg(-1), respectively. Cu, Cr, Mn, Pb and Zn were medium in variability, Mn was distributed lognormally, while Cu, Cr, Pb and Zn were distributed normally. The results of semivariance analysis showed that Mn was fit for the exponential model, Cr, Pb, Cu and Zn were fit for the linear model. The spatial distribution maps of heavy metal content of the topsoil in this city-transect were produced by means of the universal kriging interpolation. Cu was spatially distributed in ribbon, Cr and Mn were distributed in island, while the spatial distribution of Pb and Zn showed the mixed characteristic of ribbon and island. With the result of soil pollution evaluation, it showed that the pollution of Cr, Zn and Pb was relatively severe. Cr, Zn, Pb, Mn and Cu were significantly correlated, and heavy metal co-contamination existed in soil. Difference of soil heavy metals pollution along "Urban-suburban-rural" was obvious, the special variation of heavy metal concentrations in the soil closely related to the degree of industrialization and urbanization of the city.

Li-Diffusion in Spinel Li[Ni1/2Mn3/2]O4 Powder and Film Studied with μ+SR

NASA Astrophysics Data System (ADS)

Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Mukai, Kazuhiko; Cottrell, Stephen P.; Shiraki, Susumu; Hitosugi, Taro; Sassa, Yasmine; Suter, Andreas; Salman, Zaher; Prokscha, Thomas; Månsson, Martin

A dynamic behavior in spinel Li[Ni1/2Mn3/2]O4 has been studied with μ+SR measurements in film and powder samples in the temperature range between 5 and 500 K. Both samples exhibited a broad ferromagnetic transition below 120 K, indicating the random distribution of Ni and Mn ions at the octahedral 16d site. Above 150 K, the ZF-μ+SR spectrum showed a dynamic behavior well explained by a dynamic Kubo-Toyabe function. Assuming a jump diffusion of Li+ at the tetrahedral 8a site to the vacant octahedral 16c site, a diffusion coefficient of Li+ is estimated as ˜5 × 10-11 cm2/s at 300 K and ˜8 × 10-11 cm2/s at 350 K and ˜14 × 10-11 cm2/s at 400 K, with thermal activation energy Ea ˜ 0.1 eV.

Pseudocapacitive behavior of manganese oxide in lithium-ion-doped butylmethylpyrrolidinium-dicyanamide ionic liquid investigated using in situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Ming-Tsung; Li, Yun-Shan; Sun, I.-Wen; Chang, Jeng-Kuei

2014-01-01

Ideal pseudocapacitive behavior of α-MnO2 electrodes over a potential range of 3 V is found in lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)-doped butylmethylpyrrolidinium-dicyanamide (BMP-DCA) ionic liquid (IL), which is non-flammable and has a decomposition temperature of as high as ∼300 °C. Accordingly, this electrolyte is promising for high-energy, high-power, and high-safety supercapacitor applications. The addition of 0.01 M LiTFSI in the IL improves the oxide capacitance from 90 F g-1 to 120 F g-1, which is due to the incorporated Li+ ions promoting Mn valent state variation (between trivalent and tetravalent) during charge-discharge. However, excessive LiTFSI doping causes a capacitance decay due to reduced electrolyte ionic conductivity. In situ X-ray absorption spectroscopy is used to investigate the energy storage mechanism. A capacitance activation process of α-MnO2 in the Li+-doped BMP-DCA IL is found.

Core-shell structured MnSiO3 supported with CNTs as a high capacity anode for lithium-ion batteries.

PubMed

Feng, Jing; Li, Qin; Wang, Huijun; Zhang, Min; Yang, Xia; Yuan, Ruo; Chai, Yaqin

2018-04-17

Metal silicates are good candidates for use in lithium ion batteries (LIBs), however, their electrochemical performance is hindered by their poor electrical conductivity and volume expansion during Li+ insertion/desertion. In this work, one-dimensional core-shell structured MnSiO3 supported with carbon nanotubes (CNTs) (referred to as CNT@MnSiO3) with good conductivity and electrochemical performance has been successfully synthesized using a solvothermal process under moderate conditions. In contrast to traditional composites of CNTs and nanoparticles, the CNT@MnSiO3 composite in this work is made up of CNTs with a layer of MnSiO3 on the surface. The one-dimensional CNT@MnSiO3 nanotubes provide a useful channel for transferring Li+ ions during the discharge/charge process, which accelerates the Li+ diffusion speed. The CNTs inside the structure not only enhance the conductivity of the composite, but also prevent volume expansion. A high reversible capacity (920 mA h g-1 at 500 mA g-1 over 650 cycles) and good rate performance were obtained for CNT@MnSiO3, showing that this strategy of synthesizing coaxial CNT@MnSiO3 nanotubes offers a promising method for preparing other silicates for LIBs or other applications.

Elucidation of the Conversion Reaction of CoMnFeO4 Nanoparticles in Lithium Ion Battery Anode via Operando Studies.

PubMed

Permien, Stefan; Indris, Sylvio; Hansen, Anna-Lena; Scheuermann, Marco; Zahn, Dirk; Schürmann, Ulrich; Neubüser, Gero; Kienle, Lorenz; Yegudin, Eugen; Bensch, Wolfgang

2016-06-22

Conversion reactions deliver much higher capacities than intercalation/deintercalation reactions of commercial Li ion batteries. However, the complex reaction pathways of conversion reactions occurring during Li uptake and release are not entirely understood, especially the irreversible capacity loss of Mn(III)-containing oxidic spinels. Here, we report for the first time on the electrochemical Li uptake and release of Co(II)Mn(III)Fe(III)O4 spinel nanoparticles and the conversion reaction mechanisms elucidated by combined operando X-ray diffraction, operando and ex-situ X-ray absorption spectroscopy, transmission electron microscopy, (7)Li NMR, and molecular dynamics simulation. The combination of these techniques enabled uncovering the pronounced electronic changes and structural alterations on different length scales in a unique way. The spinel nanoparticles undergo a successive phase transition into a mixed monoxide caused by a movement of the reduced cations from tetrahedral to octahedral positions. While the redox reactions Fe(3+) ↔ Fe(0) and Co(2+) ↔ Co(0) occur for many charge/discharge cycles, metallic Mn nanoparticles formed during the first discharge can only be oxidized to Mn(2+) during charge. This finding explains the partial capacity loss reported for Mn(III)-based spinels. Furthermore, the results of the investigations evidence that the reaction mechanisms on the nanoscale are very different from pathways of microcrystalline materials.

Effects of Residual Lithium in the precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance

NASA Astrophysics Data System (ADS)

Jo, Minsang; Ku, Heesuk; Park, Sanghyuk; Song, Junho; Kwon, Kyungjung

2018-07-01

Li[Ni1/3Co1/3Mn1/3]O2 cathode active materials are synthesized from co-precipitated hydroxide precursors Lix[Ni1/3Co1/3Mn1/3]1-x(OH)2, and the effect of residual Li in the precursors on the lithium-ion battery (LIB) performance of their corresponding cathode active materials is investigated. Three kinds of precursors that contain different amounts of Li are selected depending on different conditions of the solution composition for the co-precipitation and washing process. It is confirmed that the introduction of Li to the precursors reduces the degree of structural perfection by X-ray diffraction analysis. Undesirable cation mixing occurs with the increasing Li content of the precursors, which is inferred from a decline in lattice parameters and the calculated intensity ratio of (003) and (104) peaks. In the voltage range of 3.0-4.3 V, the initial charge/discharge capacities and the rate capability of the cathode active materials are aggravated when Li exists in the precursors. Therefore, it could be concluded that the strict control of Li in a solution for co-precipitation of precursors is necessary in the resynthesis of cathode active materials from spent LIBs.

Electronic structure and x-ray spectroscopy of Cu2MnAl1-xGax

NASA Astrophysics Data System (ADS)

Rai, D. P.; Ekuma, C. E.; Boochani, A.; Solaymani, S.; Thapa, R. K.

2018-04-01

We explore the electronic and related properties of Cu2MnAl1-xGax with a first-principles, relativistic multiscattering Green function approach. We discuss our results in relation to existing experimental data and show that the electron-core hole interaction is essential for the description of the optical spectra especially in describing the X-ray absorption and magnetic circular dichroism spectra at the L2,3 edges of Cu and Mn.

Chemical fractionation of heavy metals in urban soils of Guangzhou, China.

PubMed

Lu, Ying; Zhu, Feng; Chen, Jie; Gan, Haihua; Guo, Yanbiao

2007-11-01

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominantly located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron-Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.

Trace metal anomalies in bleached Porites coral at Meiji Reef, tropical South China Sea

NASA Astrophysics Data System (ADS)

Li, Shu; Yu, Kefu; Zhao, Jianxin; Feng, Yuexing; Chen, Tianran

2017-01-01

Coral bleaching has generally been recognized as the main reason for tropical coral reef degradation, but there are few long-term records of coral bleaching events. In this study, trace metals including chromium (Cr), copper (Cu), molybdenum (Mo), manganese (Mn), lead (Pb), tin (Sn), titanium (Ti), vanadium (V), and yttrium (Y), were analyzed in two Porites corals collected from Meiji Reef in the tropical South China Sea (SCS) to assess differences in trace metal concentrations in bleached compared with unbleached coral growth bands. Ti, V, Cr, and Mo generally showed irregular fluctuations in both corals. Bleached layers contained high concentrations of Mn, Cu, Sn, and Pb. Unbleached layers showed moderately high concentrations of Mn and Cu only. The different distribution of trace metals in Porites may be attributable to different selectivity on the basis of vital utility or toxicity. Ti, V, Cr, and Mo are discriminated against by both coral polyps and zooxanthellae, but Mn, Cu, Sn, and Pb are accumulated by zooxanthellae and only Mn and Cu are accumulated by polyps as essential elements. The marked increase in Cu, Mn, Pb, and Sn are associated with bleaching processes, including mucus secretion, tissue retraction, and zooxanthellae expulsion and occlusion. Variation in these trace elements within the coral skeleton can be used as potential tracers of short-lived bleaching events.

Phosphorus and Cu2+ removal by periphytic biofilm stimulated by upconversion phosphors doped with Pr3+-Li.

PubMed

Zhu, Yan; Zhang, Jianhong; Zhu, Ningyuan; Tang, Jun; Liu, Junzhuo; Sun, Pengfei; Wu, Yonghong; Wong, Po Keung

2018-01-01

Upconversion phosphors (UCPs) can convert visible light into luminescence, such as UV, which can regulate the growth of microbes. Based on these fundamentals, the community composition of periphytic biofilms stimulated by UCPs doped with Pr 3+ -Li + was proposed to augment the removal of phosphorus (P) and copper (Cu). Results showed that the biofilms with community composition optimized by UCPs doped with Pr 3+ -Li + had high P and Cu 2+ removal rates. This was partly due to overall bacterial and algal abundance and biomass increases. The synergistic actions of algal, bacterial biomass and carbon metabolic capacity in the Pr-Li stimulated biofilms facilitated the removal of P and Cu 2+ . The results show that the stimulation of periphytic biofilms by lanthanide-doped UCPs is a promising approach for augmenting P and Cu 2+ removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

The deviations of the Al6Li3Cu quasicrystal from icosahedral symmetry : a reminiscence of a cubic crystal

NASA Astrophysics Data System (ADS)

Donnadieu, Patricia

1994-05-01

The (Al6Li3Cu) (T2) quasicrystals are known to exhibit large deviations from the icosahedral symmetry. Series of electron diffraction patterns are used to investigate these imperfections in as-cast T, samples. A detailed analysis of the 5-fold and 3-fold symmetry diffraction patterns shows that they are compatible with the m3 point group instead of the m35 icosahedral group. This symmetry reduction is interprétéd as reminiscent of the cubic approximant phase (R-Al5Li3Cu) rather than of higher order approximant phases. This interpretation is supported by previous observations on crystal/quasicrystal phase transformation in the AlLiCu system. Les quasicristaux de phase T2(Al6Li3Cu) montrent d'importantes déviations à la symétrie icosaédrique. Ces imperfections sont mises en évidence par diffraction électronique dans des échantillons de phase T2 brut de coulée. Un examen détaillé des diagrammes de diffraction de symétrie d'ordre 3 et 5 révèle qu'ils sont compatibles avec le groupe ponctuel m3 au lieu du groupe de l'icosaèdre (m35). Cette réduction de symétrie est interprétée comme une réminiscence de la phase cubique approximante (R-Al5Li3Cu) et non l'apparition d'approximant d'ordre plus élevé. Cette interprétation est suggérée par des observations antérieures sur la transformation cristal/quasicristal dans le système AlLiCu.

NUCLEAR HEATING IN LIF DOSEMETERS IN A FUSION NEUTRON FIELD, TRIAL OF DIRECT COMPARISON OF EXPERIMENTAL AND SIMULATED RESULTS.

PubMed

Pohorecki, Wladyslaw; Obryk, Barbara

2017-09-29

The results of nuclear heating measured by means of thermoluminescent dosemeters (TLD-LiF) in a Cu block irradiated by 14 MeV neutrons are presented. The integral Cu experiment relevant for verification of copper nuclear data at neutron energies characteristic for fusion facilities was performed in the ENEA FNG Laboratory at Frascati. Five types of TLDs were used: highly photon sensitive LiF:Mg,Cu,P (MCP-N), 7LiF:Mg,Cu,P (MCP-7) and standard, lower sensitivity LiF:Mg,Ti (MTS-N), 7LiF:Mg,Ti (MTS-7) and 6LiF:Mg,Ti (MTS-6). Calibration of the detectors was performed with gamma rays in terms of air-kerma (10 mGy of 137Cs air-kerma). Nuclear heating in the Cu block was also calculated with the use of MCNP transport code Nuclear heating in Cu and air in TLD's positions was calculated as well. The nuclear heating contribution from all simulated by MCNP6 code particles including protons, deuterons, alphas tritons and heavier ions produced by the neutron interactions were calculated. A trial of the direct comparison between experimental results and results of simulation was performed. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Lithium Metal-Copper Vanadium Oxide Battery with a Block Copolymer Electrolyte

DOE PAGES

Devaux, Didier; Wang, Xiaoya; Thelen, Jacob L.; ...

2016-09-08

Lithium (Li) batteries comprising multivalent positive active materials such as copper vanadium oxide have high theoretical capacity. These batteries with a conventional liquid electrolyte exhibit limited cycle life because of copper dissolution into the electrolyte. In this paper, we report here on the characterization of solid-state Li metal batteries with a positive electrode based on α-Cu 6.9V 6O 18.9 (α-CuVO 3). We replaced the liquid electrolyte by a nanostructured solid block copolymer electrolyte comprising of a mixture of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. In situ X-ray diffraction was used to follow the Li insertion/de-insertion mechanism into themore » α-CuVO 3 host material and its reversibility. In situ X-ray scattering revealed that the multistep electrochemical reactions involved are similar in the presence of liquid or solid electrolyte. The capacity fade of the solid-state batteries is less rapid than that of α-CuVO 3–Li metal batteries with a conventional liquid electrolyte. Hard X-ray microtomography revealed that upon cycling, voids and Cu-rich agglomerates were formed at the interface between the Li metal and the SEO electrolyte. Finally, the void volume and the volume occupied by the Cu-rich agglomerates were independent of C-rate and cycle number.« less

Enhanced electrochemical performance of Li-rich layered cathode materials via chemical activation of Li2MnO3 component and formation of spinel/carbon coating layer

NASA Astrophysics Data System (ADS)

Pang, Shengli; Xu, Kaijie; Wang, Yonggang; Shen, Xiangqian; Wang, Wenzhi; Su, Yanjing; Zhu, Meng; Xi, Xiaoming

2017-10-01

Li-rich layered oxides are promising cathode materials for advanced Li-ion batteries because of their high specific capacity and operating potential. In this work, the Li-rich layered oxide Li1·2Mn0·54Ni0·13Co0·13O2 (LMNC), is modified via a carbonization-reduction process (yielding the corresponding reduced compound denoted LMNC-R). Compared to the pristine oxide, LMNC-R delivers significantly enhanced initial discharge capacity/columbic efficiency, remarkably improved rate performance with an accelerated Li+ diffusion rate, and significantly increased capacity/voltage retention. The specific energy density and energy retention after 100 cycles increase from 378.2 Wh kg-1 and 47.7% for LMNC to 572.0 Wh kg-1 and 71.3%, respectively, for LMNC-R. The enhancement in the electrochemical performance of LMNC-R can be attributed to the synchronous formation of the oxygen non-stoichiometric Li2MnO3-δ component and to the carbon/spinel double coating layer in the material that resulted from the post-treatment process. Thus, the carbonization-reduction modification process can be used to tailor the structural evolution procedure and to suppress the metal ion dissolution of the Li-rich layered oxide during cycling.

Thermoelectric Properties of Variants of Cu4Mn2Te4 with Spinel-Related Structure.

PubMed

Guo, Quansheng; Vaney, Jean-Baptiste; Virtudazo, Raymond; Minami, Ryunosuke; Michiue, Yuichi; Yamabe-Mitarai, Yoko; Mori, Takao

2018-05-07

Thermoelectric properties of Cu 4 Mn 2 Te 4 , which is antiferromagnetic with a Néel temperature T N = 50 K and crystallizes in a spinel-related structure, have been investigated comprehensively here. The phase transition occurring at temperatures 463 and 723 K is studied by high-temperature X-ray diffraction (XRD) and differential scanning calorimetry (DSC), and its effect on thermoelectric properties is examined. Hypothetically Cu 4 Mn 2 Te 4 is semiconducting according to the formula (Cu + ) 4 (Mn 2+ ) 2 (Te 2- ) 4 , while experimentally it shows p-type metallic conduction behavior, exhibiting electrical conductivity σ = 2500 Ω -1 cm -1 and Seebeck coefficient α = 20 μV K -1 at 325 K. Herein, we show that the carrier concentration and thus the thermoelectric transport properties could be further optimized through adding electron donors such as excess Mn. Discussions are made on the physical parameters contributing to the low thermal conductivity, including Debye temperature, speed of sound, and the Grüneisen parameter. As a result of simultaneously boosted power factor and reduced thermal conductivity, a moderately high zT = 0.65 at 680 K is obtained in an excess Mn\\In co-added sample, amounting to 5 times that of the pristine Cu 4 Mn 2 Te 4 . This value ( zT = 0.65) is the best result ever reported for spinel and spinel-related chalcogenides.

Synthesis and characterization of spinel type high-power cathode materials Li MxMn2-x O4 (M=Ni, Co, Cr)

NASA Astrophysics Data System (ADS)

Yoon, Y. K.; Park, C. W.; Ahn, H. Y.; Kim, D. H.; Lee, Y. S.; Kim, J.

2007-05-01

The transition metal-doped spinel cathode materials, LiM0.5Mn1.5O4 (M=Ni. Co, Cr) were prepared by solid-state reaction. The structure and morphology of the samples were investigated by X-ray diffraction, Rietveld refinement and scanning electron microscopy (SEM). The diffraction peaks of all the samples corresponded to a single phase of cubic spinel structure with a space group Fd3m. Field-emission SEM shows octahedron like shapes and the primary particles size was between 500 nm and 2 μm. Oxidation states of Ni, Co and Cr were found to be 2+, 2+ and 3+ as revealed by X-ray photoelectron spectroscopy. During discharging, LiNi0.5Mn1.5O4 and LiCo0.5Mn1.5O4 sample shows more than 130 mAh/g between 3.5 and 5.2 V at a current density of 0.65 mA/cm2 and well developed plateau around 5 V, respectively.

A High‐Voltage and High‐Capacity Li1+xNi0.5Mn1.5O4 Cathode Material: From Synthesis to Full Lithium‐Ion Cells

PubMed Central

Mancini, Marilena; Gabrielli, Giulio; Kinyanjui, Michael; Kaiser, Ute; Wohlfahrt‐Mehrens, Margret

2016-01-01

Abstract We report Co‐free, Li‐rich Li1+xNi0.5Mn1.5O4 (0

Self-Substitution and the Temperature Effects on the Electrochemical Performance in the High Voltage Cathode System LiMn 1.5+xNi 0.5-xO 4 (x = 0.1)

DOE PAGES

Xu, Yun; Zhao, Mingyang; Khalid, Syed; ...

2017-05-09

The high voltage cathode material, LiMn 1.6Ni 0.4O 4, was prepared by a polymer-assisted method. The novelty of this paper is the substitution of Ni with Mn, which already exists in the crystal structure instead of other isovalent metal ion dopants which would result in capacity loss. The electrochemical performance testing including stability and rate capability was evaluated. The temperature was found to impose a change on the valence and structure of the cathode materials. Specifically, manganese tends to be reduced at a high temperature of 800 °C and leads to structural changes. The manganese substituted LiMn 1.5Ni 0.5O 4more » (LMN) has proved to be a good candidate material for Li-ion battery cathodes displaying good rate capability and capacity retention. Finally, the cathode materials processed at 550 °C showed a stable performance with negligible capacity loss for 400 cycles.« less

Giant magnetic coercivity in CaCu{sub 5}-type SmNi{sub 3}TSi (T=Mn–Cu) solid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Jinlei; Yan, Xu; Morozkin, A.V., E-mail: morozkin@tech.chem.msu.ru

The effects of transition metal substitution for Ni on the magnetic properties of the CaCu{sub 5}-type SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) solid solutions have been investigated. SmNi{sub 3}MnSi, SmNi{sub 3}FeSi, SmNi{sub 3}CoSi and SmNi{sub 3}CuSi show ferromagnetic ordering at 125 K, 190 K, 46 K and 12 K and field induced transitions at 65 K, 110 K, 30 K and 6 K, respectively. The magnetocaloric effects of SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) were calculated in terms of isothermal magnetic entropy change (ΔS{sub m}). The magnetic entropy ΔS{sub m} reaches value of −1.1 J/kg K at 130 K formore » SmNi{sub 3}MnSi, −0.4 J/kg K at 180 K for SmNi{sub 3}FeSi, −0.37 J/kg K at 45 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 12 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the ferromagnetic ordering temperature. They show positive ΔS{sub m} of +2.4 J/kg K at 30 K for SmNi{sub 3}MnSi, −2.6 J/kg K at 65 K for SmNi{sub 3}FeSi, +0.73 J/kg K at 15 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 6 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the metamagnetic-like transition temperature. Below the field induced transition temperature, SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) exhibits giant magnetic coercivity of 80 kOe at 20 K for SmNi{sub 3}MnSi, 87 kOe at 40 K for SmNi{sub 3}FeSi, 27 kOe at 20 K for SmNi{sub 3}CoSi and 54 kOe at 5 K for SmNi{sub 3}CuSi. - Graphical abstract: CaCu{sub 5}-type SmNi{sub 3}MnSi, SmNi{sub 3}FeSi, SmNi{sub 3}CoSi and SmNi{sub 3}CuSi show ferromagnetic ordering at 125 K, 190 K, 46 K and 12 K and field induced transitions at 65 K, 110 K, 30 K and 6 K, respectively. The magnetic entropy ΔS{sub m} reaches value of −1.1 J/kg K at 130 K for SmNi{sub 3}MnSi, −0.4 J/kg K at 180 K for SmNi{sub 3}FeSi, −0.37 J/kg K at 45 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 12 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the ferromagnetic ordering temperature. They show positive ΔS{sub m} of +2.4 J/kg K at 30 K for SmNi{sub 3}MnSi, −2.6 J/kg K at 65 K for SmNi{sub 3}FeSi, +0.73 J/kg K at 15 K for SmNi{sub 3}CoSi and −0.5 J/kg K at 6 K for SmNi{sub 3}CuSi in field change of 0–50 kOe around the metamagnetic-like transition temperature. Below the field induced transition temperature, SmNi{sub 3}TSi (T=Mn, Fe, Co, Cu) exhibits giant magnetic coercivity of 80 kOe at 20 K for SmNi{sub 3}MnSi, 87 kOe at 40 K for SmNi{sub 3}FeSi, 27 kOe at 20 K for SmNi{sub 3}CoSi and 54 kOe at 5 K for SmNi{sub 3}CuSi. - Highlights: • CaCu{sub 5}-type SmNi{sub 3}{Mn, Fe, Co, Cu}Si exhibit the Curie points at 12–190 K. • SmNi{sub 3}{Mn, Fe, Co, Cu}Si show field induced transition at 6–110 K. • SmNi{sub 3}MnSi shows huge magnetic hysteresis with coercive field of 80 kOe at 20 K. • SmNi{sub 3}FeSi shows huge magnetic hysteresis with coercive field of 87 kOe at 40 K. • SmNi{sub 3}CuSi shows giant coercive field of 54 kOe at 5 K.« less

Geographic and Oceanographic Information within Trace Metals in Moray Eel Otoliths

NASA Astrophysics Data System (ADS)

Savidge, W.; Windom, H.; Buck, C.

2016-02-01

Adult moray eels exhibit high site fidelity to particular reefs. We hypothesized that the trace metal composition of otoliths of eels could potentially provide insight into gradients in oceanographic processes on the South Atlantic Bight continental shelf where eels are resident on patchy hardbottom reefs throughout the entire region. Otoliths of moray eels collected from the mid-shelf of South Carolina were examined for their trace metal composition (Ba, Sr, Pb, Cu, Li, Mg, V, Mn, Zn). Samples were broadly lumped into four regions: "North," "North Cape Romain," "South Cape Romain," and "South". Trace metal composition within otoliths showed no latitudinal trends. However, factor analysis of the trace metals revealed that otoliths from the South Cape Romain region appeared as a compositionally distinct subgroup, based primarily on their Li and Mg content. Recent work on corals (Montagna et al. 2014) has shown the Li/Mg ratio within coral skeletons is sensitive to calcification temperature and can be used as a paleothermometer. If analogous processes influence Li/Mg ratios within otoliths, the data suggest that the bottom water at the South Cape Romain site is colder than other locations along the South Carolina shelf, perhaps as a result of locally enhanced upwelling. Additional samples from NC, SC, GA, and FL are being examined to see if other sites within the South Atlantic Bight show similar patterns. Montagna, P., McCulloch, M., Douville, E., et al. 2014. Li/Mg systematics in scleratinian corals: Calibration of the thermometer. Geochim Cosmochim Acta 132: 288-310.

Copper brain protein protection against free radical-induced neuronal death: Survival ratio in SH-SY5Y neuroblastoma cell cultures.

PubMed

Deloncle, Roger; Fauconneau, Bernard; Guillard, Olivier; Delaval, José; Lesage, Gérard; Pineau, Alain

2017-01-01

In Creutzfeldt Jakob, Alzheimer and Parkinson diseases, copper metalloproteins such as prion, amyloid protein precursor and α-synuclein are able to protect against free radicals by reduction from cupric Cu +2 to cupreous Cu + . In these pathologies, a regional copper (Cu) brain decrease correlated with an iron, zinc or manganese (Mn) increase has previously been observed, leading to local neuronal death and abnormal deposition of these metalloproteins in β-sheet structures. In this study we demonstrate the protective effect of Cu metalloproteins against deleterious free-radical effects. With neuroblastoma SH-SY5Y cell cultures, we show that bovine brain prion protein in Cu but not Mn form prevents free radical-induced neuronal death. The survival ratio of SH-SY5Y cells has been measured after UV irradiation (free radical production), when the incubating medium is supplemented with bovine brain homogenate in native, Cu or Mn forms. This ratio, about 28% without any addition or with bovine brain protein added in Mn form, increases by as much as 54.73% with addition to the culture medium of native bovine brain protein and by as much as 95.95% if the addition is carried out in cupric form. This protective effect of brain copper protein against free radical-induced neuronal death has been confirmed with Inductively Coupled Plasma Mass Spectrometry Mn and Cu measurement in bovine brain homogenates: respectively lower than detection limit and 9.01μg/g dry weight for native form; lower than detection limit and 825.85μg/g dry weight for Cu-supplemented form and 1.75 and 68.1μg/g dry weight in Mn-supplemented brain homogenate. Copyright © 2016 Elsevier GmbH. All rights reserved.

Synthesis of KMnO4-treated magnetic graphene oxide nanocomposite (Fe3O4@GO/MnO x ) and its application for removing of Cu2+ ions from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Huining; Chang, Qing; Jiang, Yu; Li, Huili; Yang, Yahong

2018-04-01

A magnetic KMnO4-treated graphene-oxide-based nanocomposite, Fe3O4@GO/MnO x , was synthesized through a facile hydrothermal technique. The properties of the Fe3O4@GO/MnO x nanocomposite were characterized by SEM, XRD and FTIR. Batch experiments showed that the maximum adsorption capacity calculated by the Langmuir model for Cu2+ was 62.65 mg g-1 at T = 303.15 K. Kinetics and XPS analysis also revealed that the mechanism of Cu2+ removal was mainly a chemical adsorption process involving both the MnO x particles and oxygen functional groups. The prepared Fe3O4@GO/MnO x was found to be an ideal adsorbent for the removal of Cu2+ ions due to the MnO x particle coating, and was easily separated using a magnetic field after utilization. Reusability studies imply that Fe3O4@GO/MnO x is a suitable material for heavy metal ion removal from aqueous solutions in real applications.

Effect of Mn and AlTiB Addition and Heattreatment on the Microstructures and Mechanical Properties of Al-Si-Fe-Cu-Zr Alloy.

PubMed

Yoo, Hyo-Sang; Kim, Yong-Ho; Lee, Seong-Hee; Son, Hyeon-Taek

2018-09-01

The microstructure and mechanical properties of as-extruded Al-0.1 wt%Si-0.2 wt%Fe- 0.4 wt%Cu-0.04 wt%Zr-xMn-xAlTiB (x = 1.0 wt%) alloys under various annealing processes were investigated and compared. After the as-cast billets were kept at 400 °C for 1 hr, hot extrusion was carried out with a reduction ratio of 38:1. In the case of the as-extruded Al-Si-Fe-Cu-Zr alloy at annealed at 620 °C, large equiaxed grain was observed. When the Mn content is 1.0 wt%, the phase exhibits a skeleton morphology, the phase formation in which Mn participated. Also, the volume fraction of the intermetallic compounds increased with Mn and AlTiB addition. For the Al-0.1Si-0.2Fe-0.4Cu-0.04Zr alloy with Mn and AlTiB addition from 1.0 wt%, the ultimate tensile strength increased from 100.47 to 119.41 to 110.49 MPa. The tensile strength of the as-extruded alloys improved with the addition of Mn and AlTiB due to the formation of Mn and AlTiB-containing intermetallic compounds.

CuMn1.8O4 protective coatings on metallic interconnects for prevention of Cr-poisoning in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sun, Zhihao; Wang, Ruofan; Nikiforov, Alexey Y.; Gopalan, Srikanth; Pal, Uday B.; Basu, Soumendra N.

2018-02-01

Cr-poisoning of the cathodes due to the presence of metallic interconnects is detrimental to the performance of intermediate temperature solid oxide fuel cell stacks. Applying a protective coating on the interconnect is an effective solution to preventing Cr-poisoning. In this study, the application of a protective CuMn1.8O4 spinel coating is explored. Dense coatings are deposited on both metallic flat plates and meshes by electrophoretic deposition followed by thermal densification steps. The coating is found to be a mixture of Mn3O4 and cubic spinel phases at room temperature but is a pure cubic spinel phase between 750 °C and 850 °C. A reaction layer between the Cr2O3 scale at the coating/interconnect interface and CuMn1.8O4 coating is found to be a mixture of (Cu,Mn,Cr)3-xO4 cubic spinel phases with Cr-rich precipitates believed to be Cr2O3, indicating that the coating layer acts as a Cr getter. Solubility experiments show that 1 mol of the CuMn1.8O4 phase can getter at least 1.83 mol of Cr2O3 at 800 °C. Electrochemical testing of cells in the presence of coated interconnects show that the CuMn1.8O4 coating getters Cr effectively for 12 days at 800 °C, leading to no performance loss of the cell due to Cr-poisoning.

Comparative trace elemental analysis of cancerous and non-cancerous tissues of rectal cancer patients using PIXE

NASA Astrophysics Data System (ADS)

Naga Raju, G. J.; Sarita, P.; Murthy, K. S. R.

2017-08-01

Particle Induced X-ray Emission (PIXE), an accelerator based analytical technique has been employed in this work for the analysis of trace elements in the cancerous and non-cancerous tissues of rectal cancer patients. A beam of 3 MeV protons generated from 3 MV Pelletron accelerator at the Ion Beam Laboratory of Institute of Physics, Bhubaneswar, India was used as projectile to excite the atoms present in the tissues samples. PIXE technique, with its capability to detect simultaneously several elements present at very low concentrations, offers an excellent tool for trace element analysis. The characteristic X-rays emitted by the samples were recorded by a high resolution Si (Li) detector. On the basis of the PIXE spectrum obtained for each sample, the elements Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Br were identified and their relative concentrations were estimated in the cancerous and non-cancerous tissues of rectum. The levels of Mn, Fe, Co, Cu, Zn, and As were higher (p < 0.005) while the levels of Ca, Cr and Ni were lower (p < 0.005) in the cancer tissues relative to the normal tissues. The alterations in the levels of the trace elements observed in the present work are discussed in this paper with respect to their potential role in the initiation, promotion and inhibition of cancer of the rectum.

Combination of lightweight elements and nanostructured materials for batteries.

PubMed

Chen, Jun; Cheng, Fangyi

2009-06-16

In a society that increasingly relies on mobile electronics, demand is rapidly growing for both primary and rechargeable batteries that power devices from cell phones to vehicles. Existing batteries utilize lightweight active materials that use electrochemical reactions of ions such as H(+), OH(-) and Li(+)/Mg(2+) to facilitate energy storage and conversion. Ideal batteries should be inexpensive, have high energy density, and be made from environmentally friendly materials; batteries based on bulk active materials do not meet these requirements. Because of slow electrode process kinetics and low-rate ionic diffusion/migration, most conventional batteries demonstrate huge gaps between their theoretical and practical performance. Therefore, efforts are underway to improve existing battery technologies and develop new electrode reactions for the next generation of electrochemical devices. Advances in electrochemistry, surface science, and materials chemistry are leading to the use of nanomaterials for efficient energy storage and conversion. Nanostructures offer advantages over comparable bulk materials in improving battery performance. This Account summarizes our progress in battery development using a combination of lightweight elements and nanostructured materials. We highlight the benefits of nanostructured active materials for primary zinc-manganese dioxide (Zn-Mn), lithium-manganese dioxide (Li-Mn), and metal (Mg, Al, Zn)-air batteries, as well as rechargeable lithium ion (Li-ion) and nickel-metal hydride (Ni-MH) batteries. Through selected examples, we illustrate the effect of structure, shape, and size on the electrochemical properties of electrode materials. Because of their numerous active sites and facile electronic/ionic transfer and diffusion, nanostructures can improve battery efficiency. In particular, we demonstrate the properties of nanostructured active materials including Mg, Al, Si, Zn, MnO(2), CuV(2)O(6), LiNi(0.8)Co(0.2)O(2), LiFePO(4), Fe(2)O(3), Co(3)O(4), TiS(2), and Ni(OH)(2) in battery applications. Electrochemical investigations reveal that we generally attain larger capacities and improved kinetics for electrode materials as their average particle size decreases. Novel nanostructures such as nanowires, nanotubes, nanourchins, and porous nanospheres show lower activation energy, enhanced reactivity, improved high-rate charge/discharge capability, and more controlled structural flexibility than their bulk counterparts. In particular, anode materials such as Si nanospheres and Fe(2)O(3) nanotubes can deliver reversible capacity exceeding 500 mA.h/g. (Graphite used commercially has a theoretical capacity of 372 mA x h/g.) Nanocomposite cathode materials such as NiP-doped LiFePO(4) and metal hydroxide-coated Ni(OH)(2) nanotubes allow us to integrate functional components, which enhance electrical conductivity and suppress volume expansion. Therefore, shifting from bulk to nanostructured electrode materials could offer a revolutionary opportunity to develop advanced green batteries with large capacity, high energy and power density, and long cycle life.

Baseline element concentrations in soils and plants, Wattenmeer National Park, North and East Frisian Islands, Federal Republic of Germany

USGS Publications Warehouse

Severson, R.C.; Gough, L.P.; van den Boom, G.

1992-01-01

Baseline element concentrations are given for dune grass (Ammophilia arenaria), willow (Salix repens), moss (Hylocomium splendens) and associated surface soils. Baseline and variability data for pH, ash, Al, As, Ba, C, Ca, Cd, Ce, Co, Cr, Cu, Fe, Hg, K, La, Li, Mg, Mn, Na, Nb, Nd, Ni, P, Pb, S, Sc, Se, Sr, Th, Ti, V, Y, Yb, and Zn are reported; however, not all variables are reported for all media because, in some media, certain elements were below the analytical detection limit. Spatial variation in element concentration between five Frisian Islands are given for each of the sample media. In general, only a few elements in each media showed statistically significant differences between the islands sampled. The measured concentrations in all sample media exhibited ranges that cannot be attributed to anthropogenic additions of trace elements, with the possible exception of Hg and Pb in surface soils.Baseline element concentrations are given for dune grass (Ammophilia arenaria), willow (Salix repens), moss (Hylocomium splendens) and associated surface soils. Baseline and variability data for pH, ash, Al, As, Ba, C, Ca, Cd, Ce, Co, Cr, Cu, Fe, Hg, K, La, Li, Mg, Mn, Na, Nb, Nd, Ni, P, Pb, S, Sc, Se, Sr, Th, Ti, V, Y, Yb, and Zn are reported; however, not all variables are reported for all media because, in some media, certain elements were below the analytical detection limit. Spatial variation in element concentration between five Frisian Islands are given for each of the sample media. In general, only a few elements in each media showed statistically significant differences between the islands sampled. The measured concentrations in all sample media exhibited ranges that cannot be attributed to anthropogenic additions of trace elements, with the possible exception of Hg and Pb in surface soils.