High performance Li-ion sulfur batteries enabled by intercalation chemistry.

PubMed

Lv, Dongping; Yan, Pengfei; Shao, Yuyan; Li, Qiuyan; Ferrara, Seth; Pan, Huilin; Graff, Gordon L; Polzin, Bryant; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

2015-09-11

The unstable interface of lithium metal in high energy density Li sulfur (Li-S) batteries raises concerns of poor cycling, low efficiency and safety issues, which may be addressed by using intercalation types of anode. Herein, a new prototype of Li-ion sulfur battery with high performance has been demonstrated by coupling a graphite anode with a sulfur cathode (2 mA h cm(-2)) after successfully addressing the interface issue of graphite in an ether based electrolyte.

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.

Theory of a quantum spin liquid in the hydrogen-intercalated honeycomb iridate H3LiIr2O6

NASA Astrophysics Data System (ADS)

Slagle, Kevin; Choi, Wonjune; Chern, Li Ern; Kim, Yong Baek

2018-03-01

We propose a theoretical model for a gapless spin liquid phase that may have been observed in a recent experiment on H3LiIr2O6 . Despite the insulating and nonmagnetic nature of the material, the specific heat coefficient C /T ˜1 /√{T } in zero magnetic field and C /T ˜T /B3 /2 with finite magnetic field B have been observed. In addition, the NMR relaxation rate shows 1 /(T1T ) ˜(C/T ) 2 . Motivated by the fact that the interlayer/in-plane lattice parameters are reduced/elongated by the hydrogen intercalation of the parent compound Li2IrO3 , we consider four layers of the Kitaev honeycomb lattice model with additional interlayer exchange interactions. It is shown that the resulting spin liquid excitations reside mostly in the top and bottom layers of such a layered structure and possess a quartic dispersion. In an applied magnetic field, each quartic mode is split into four Majorana cones with the velocity v ˜B3 /4 . We suggest that the spin liquid phase in these "defect" layers, placed between different stacking patterns of the honeycomb layers, can explain the major phenomenology of the experiment, which can be taken as evidence that the Kitaev interaction plays the primary role in the formation of a quantum spin liquid in this material.

Constructing a novel and safer energy storing system using a graphite cathode and a MoO 3 anode

NASA Astrophysics Data System (ADS)

Gunawardhana, Nanda; Park, Gum-Jae; Dimov, Nikolay; Thapa, Arjun Kumar; Nakamura, Hiroyoshi; Wang, Hongyu; Ishihara, Tatsumi; Yoshio, Masaki

A cell employing a graphite cathode and a molybdenum (VI) oxide (MoO 3) anode is investigated as a possible energy storage device. Graphite cathode allows raising the voltage well above the cathode materials of LIBs without causing safety issues. The bottom potential of this anode is 2.0 V vs. Li/Li +, which is well above the lithium plating potential. Pulse polarization experiment reveals that no lithium deposition occurs, which further enhances the safety of the graphite/MoO 3 full cell. Charge/discharge mechanism of this system results from intercalation and de-intercalation of the PF 6 - in the cathode (KS-6) and Li + in the anode (MoO 3). This mechanism is supported by in situ X-ray diffraction data of the graphite/MoO 3 cell recorded at various states of charge.

Graphite intercalation compound with iodine as the major intercalate

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Kucera, Donald

1994-01-01

Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries.

PubMed

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Ma, Jianmin; Deng, Yonghong; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-10-01

Lithium-ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium-ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated-graphite for LIBs, but also an effective strategy to develop diverse high-energy batteries for stationary energy storage in the future.

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen; Prisko, Aniko

1999-01-01

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Graphite intercalation with fluoroanions by chemical and electrochemical methods

NASA Astrophysics Data System (ADS)

Ozmen-Monkul, Bahar

New acceptor-type graphite intercalation compounds (GICs) containing perfluoroalkyl anions have been synthesized by using both chemical and electrochemical methods and characterized by elemental and thermogravimetric analyses. Investigation into these graphite intercalation compounds can provide novel materials and a detailed understanding of their properties. GICs of composition Cx[FB(C2F 5)3]·deltaF are prepared for the first time by the intercalation of fluoro-tris(pentafluoroethyl)borate anion, [FB(C2F 5)3]-, under ambient conditions in aqueous (48%) hydrofluoric acid containing the oxidant K2[MnF6]. Powder-XRD data indicate that products are pure stage 2 and physical mixture of stage 2 and stage 3 after 1 h to 20 h reaction times. The calculated basal repeat distance, Ic, is 1.20 nm for stage 2 and 1.54-1.56 nm for stage 3 GICs, corresponding to gallery heights of di = 0.86-0.89 nm. In addition, stage 2 GIC of C x[FB(C2F5)3]·deltaCH 3NO2 having di = 0.84 nm is prepared by electrochemical oxidation of graphite in a nitromethane electrolyte. The elemental analyses of these complex GICs required that a new sample digestion protocol be developed. After digestion, the fluoride amounts in these GIC samples were analyzed by using ion-selective fluoride combination electrode. The method developed is able to provide fluoride anion content in GICs without interference from the decomposition products of [FB(C 2F5)3]- anion. For the boron analyses the same digestion procedure above is used and the B contents were determined by ICP-AES. For Cx[FB(C2F 5)3]·deltaF, both compositional parameters x and delta are obtained from the results of elemental B and F analyses. For the chemically prepared GICs at 1 h to 20 h, calculated x values were in the range of 51-56 and the calculated delta values increased with reaction time from approx. 0-2. Combining B analysis and TGA mass loss gives a composition of x = 44 and delta = 0.37 for the electrochemically prepared GIC of Cx[FB(C2

Heat-Storage Modules Containing LiNO3-3H2O and Graphite Foam

NASA Technical Reports Server (NTRS)

Bootle, John

2008-01-01

A heat-storage module based on a commercial open-cell graphite foam (Poco-Foam or equivalent) imbued with lithium nitrate trihydrate (LiNO3-3H2O) has been developed as a prototype of other such modules for use as short-term heat sources or heat sinks in the temperature range of approximately 28 to 30 C. In this module, the LiNO3-3H2O serves as a phase-change heat-storage material and the graphite foam as thermally conductive filler for transferring heat to or from the phase-change material. In comparison with typical prior heat-storage modules in which paraffins are the phase-change materials and aluminum fins are the thermally conductive fillers, this module has more than twice the heat-storage capacity per unit volume.

Self-Activating, Capacitive Anion Intercalation Enables High-Power Graphite Cathodes.

PubMed

Wang, Gang; Yu, Minghao; Wang, Jungang; Li, Debao; Tan, Deming; Löffler, Markus; Zhuang, Xiaodong; Müllen, Klaus; Feng, Xinliang

2018-05-01

Developing high-power cathodes is crucial to construct next-generation quick-charge batteries for electric transportation and grid applications. However, this mainly relies on nanoengineering strategies at the expense of low scalability and high battery cost. Another option is provided herein to build high-power cathodes by exploiting inexpensive bulk graphite as the active electrode material, where anion intercalation is involved. With the assistance of a strong alginate binder, the disintegration problem of graphite cathodes due to the large volume variation of >130% is well suppressed, making it possible to investigate the intrinsic electrochemical behavior and to elucidate the charge storage kinetics of graphite cathodes. Ultrahigh power capability up to 42.9 kW kg -1 at the energy density of >300 Wh kg -1 (based on graphite mass) and long cycling life over 10 000 cycles are achieved, much higher than those of conventional cathode materials for Li-ion batteries. A self-activating and capacitive anion intercalation into graphite is discovered for the first time, making graphite a new intrinsic intercalation-pseudocapacitance cathode material. The finding highlights the kinetical difference of anion intercalation (as cathode) from cation intercalation (as anode) into graphitic carbon materials, and new high-power energy storage devices will be inspired. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Li15Al3Si6 (Li14.6Al3.4Si6), a compound displaying a heterographite-like anionic framework.

PubMed

Spina, Laurent; Tillard, Monique; Belin, Claude

2003-02-01

The title compound, lithium aluminium silicide (15/3/6), crystallizes in the hexagonal centrosymmetric space group P6(3)/m. The three-dimensional structure of this ternary compound may be depicted as two interpenetrating lattices, namely a graphite-like Li(3)Al(3)Si(6) layer and a distorted diamond-like lithium lattice. As is commonly found for LiAl alloys, the Li and Al atoms are found to share some crystallographic sites. The diamond-like lattice is built up of Li cations, and the graphite-like anionic layer is composed of Si, Al and Li atoms in which Si and Al are covalently bonded [Si-Al = 2.4672 (4) A].

(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).

Li(x)FeF6 (x = 2, 3, 4) battery materials: structural, electronic and lithium diffusion properties.

PubMed

Schroeder, Melanie; Eames, Christopher; Tompsett, David A; Lieser, Georg; Islam, M Saiful

2013-12-21

Lithium iron fluoride materials have attracted recent interest as cathode materials for lithium ion batteries. The electrochemical properties of the high energy density Li(x)FeF6 (x = 2, 3, 4) materials have been evaluated using a combination of potential-based and DFT computational methods. Voltages of 6.1 V and 3.0 V are found for lithium intercalation from Li2FeF6 to α-Li3FeF6 and α-Li3FeF6 to Li4FeF6 respectively. The calculated density of states indicate that Li2FeF6 possesses metallic states that become strongly insulating after lithium intercalation to form α-Li3FeF6. The large energy gain associated with this metal-insulator transition is likely to contribute to the associated large voltage of 6.1 V. Molecular dynamics simulations of lithium diffusion in α-Li3FeF6 at typical battery operating temperatures indicate high lithium-ion mobility with low activation barriers. These results suggest the potential for good rate performance of lithium iron fluoride cathode materials.

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate.

PubMed

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-12-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy (μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO 4 , K 2 Cr 2 O 7 ) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO 4 and NaClO 3 .

Synthesis and Characterization of Highly Intercalated Graphite Bisulfate

NASA Astrophysics Data System (ADS)

Salvatore, Marcella; Carotenuto, Gianfranco; De Nicola, Sergio; Camerlingo, Carlo; Ambrogi, Veronica; Carfagna, Cosimo

2017-03-01

Different chemical formulations for the synthesis of highly intercalated graphite bisulfate have been tested. In particular, nitric acid, potassium nitrate, potassium dichromate, potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide have been used in this synthesis scheme as the auxiliary reagent (oxidizing agent). In order to evaluate the presence of delamination, and pre-expansion phenomena, and the achieved intercalation degree in the prepared samples, the obtained graphite intercalation compounds have been characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), infrared spectroscopy (FT-IR), micro-Raman spectroscopy ( μ-RS), and thermal analysis (TGA). Delamination and pre-expansion phenomena were observed only for nitric acid, sodium chlorate, and hydrogen peroxide, while the presence of strong oxidizers (KMnO4, K2Cr2O7) led to stable graphite intercalation compounds. The largest content of intercalated bisulfate is achieved in the intercalated compounds obtained from NaIO4 and NaClO3.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)‐Ion Batteries

PubMed Central

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-01-01

Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future. PMID:29051856

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

NASA Technical Reports Server (NTRS)

West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

2007-01-01

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

Functional interface of polymer modified graphite anode

NASA Astrophysics Data System (ADS)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

New Lithium- and Diamine-Intercalated Superconductors Lix(CnH2n+4N2)yMoSe2 (n = 2,6)

NASA Astrophysics Data System (ADS)

Sato, Kazuki; Noji, Takashi; Hatakeda, Takehiro; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

2018-05-01

We have succeeded in synthesizing new intercalation superconductors Lix(C2H8N2)yMoSe2 and Lix(C6H16N2)yMoSe2 with Tc = 4.2 and 3.8-6.0 K, respectively, via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into semiconducting 2H-MoSe2. It has been found that the Tc values are related not to the interlayer spacing between MoSe2 layers so much but to the electronic density of states (EDOS) at the Fermi level. Moreover, only Li-intercalated LixMoSe2 with a small interlayer spacing has been found to be non-superconducting. Accordingly, it has been concluded that not only a sufficient amount of EDOS at the Fermi level due to the charge transfer from intercalated Li to MoSe2 layers but also the enhancement of the two-dimensionality of the crystal structure and/or electronic structure due to the expansion of the interlayer spacing between MoSe2 layers is necessary for the appearance of superconductivity in MoSe2-based intercalation superconductors. The pairing mechanism and the analogy to the superconductivity in the electric double-layer transistors of 2H-MoX2 (X = S, Se, Te) are discussed.

Electrochemical characterisation of CaCl2 deficient LiCl-KCl-CaCl2 eutectic melt and electro-deoxidation of solid UO2

NASA Astrophysics Data System (ADS)

Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K. S.; Nagarajan, K.

2016-03-01

The CaCl2 deficient ternary eutectic melt LiCl-KCl-CaCl2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K-923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca2+ ions followed by Li+ ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca2+ and Li+ was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low-energy reactions occurring on the UO2 electrode in the melt. UO2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal.

Enhanced Emission from Li2CaSiO4:Dy3+ Phosphors by Doping with Al3+ and B3+

NASA Astrophysics Data System (ADS)

Erdoğmuş, E.

2016-05-01

Pure Li2CaSiO4, Li2CaSiO4:Dy3+ and Al3+, B3+ co-doped materials were prepared by a solid-state reaction in air at 900°C for 6 h and characterized by using powder XRD. The luminescence properties of the synthesized phosphors were measured at room temperature with a spectrofluorometer. Li2CaSiO4:Dy3+ emits at 484, 575, and 660 nm upon 352 nm excitation. The emission spectrum intensity of Dy3+ increased from 0.01 to 0.06 mol.%, and beyond 0.06 mol.%, concentration quenching was observed. Also, in this study, the effects of boric acid and aluminum oxide concentration on the photoluminescence properties of Dy3+ doped phosphors were investigated. The results showed that boric acid and aluminum oxide were effective in improving the photoluminescence intensity of Li2CaSiO4:Dy3+ compounds.

Graphite fiber intercalation: Dynamics of the bromine intercalation process

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Zinolabedini, R.

1985-01-01

The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

Temperature compensation effects of TiO2 on Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ microwave dielectric ceramic

NASA Astrophysics Data System (ADS)

Hu, Mingzhe; Wei, Huanghe; Xiao, Lihua; Zhang, Kesheng; Hao, Yongde

2017-10-01

The crystal structure and dielectric properties of TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ microwave ceramics are investigated in the present paper. The crystal structure is probed by XRD patterns and their Rietveld refinement, results show that a single perovskite phase is formed in TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramics with the crystal structure belonging to the orthorhombic Pbnm 62 space group. Raman spectra results indicate that the B-site order-disorder structure transition is a key point to the dielectric loss of TiO2-modified Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramics at microwave frequencies. After properly modified by TiO2, the large negative temperature coefficient of Ca[(Li1/3Nb2/3)0.8Sn0.2]O3-δ ceramic can be compensated and the optimal microwave dielectric properties can reach 𝜀r = 25.66, Qf = 18,894 GHz and TCF = -6.3 ppm/∘C when sintered at 1170∘C for 2.5 h, which manifests itself for potential use in microwave dielectric devices for modern wireless communication.

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.

Preparation of graphite intercalation compounds containing oligo and polyethers

NASA Astrophysics Data System (ADS)

Zhang, Hanyang; Lerner, Michael M.

2016-02-01

Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets.Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets. Electronic supplementary information (ESI) available: Domain size, additional Raman spectra info, compositional calculation, and packing fractions. See DOI: 10.1039/c5

C-13 nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The C-13 NMR chemical shifts of graphite intercalation compounds have been calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about - 140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal-conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

First-Principles evaluation of the Chevrel phase intercalated with Be, Mg, Ca, Sr, and Ba

NASA Astrophysics Data System (ADS)

Juran, Taylor; Smeu, Manuel

Li ion batteries are extremely useful when an item requires portability and compactness, such as laptops and cell phones; due to the lightweight/compact nature of Li ion batteries. The lightweight and compact nature of Li ion batteries comes at a high cost. It is sensible to consider Li ion battery alternatives, which are more cost effective and useable when portability is not a priority. An option for a less expensive battery source is the Ca ion battery. The Ca ion battery is interesting as many researchers overlook the potential battery source due to the perplexity of finding suitable anode materials and electrolytes. In order for this technology to work, cathodes that allow for the reversible intercalation of Ca2+ ions and also provide a preferred voltage must be identified. We investigate the Chevrel phase compounds of Mo6X8 (X = S, Se, Te) which can intercalate various ions. The concentration of the ion intercalated with the Chevrel cathode is studied. We consider doped versions of the Chevrel phase, using various dopants to substitute Mo. We use density functional theory to calculate the voltage of several intercalation ions with the Chevrel material. The resulting electronic properties of the aforementioned materials will be investigated.

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

PubMed

Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

2016-06-29

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Shaffer, Nanette

1987-01-01

Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.

1987-01-01

A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

STM/STS studies of Ca-intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Shimizu, Ryota; Sugawara, Katsuaki; Kanetani, Kohei; Iwaya, Katsuya; Sato, Takafumi; Takahashi, Takashi; Hitosugi, Taro

2013-03-01

We have performed low temperature scanning tunneling microscopy/spectroscopy (STM/STS) measurements on a two-dimensional Ca-intercalated bilayer graphene epitaxially grown on a 6H-SiC(0001) substrate. The STM topographic images clearly resolve each intercalated Ca atom with graphene-based honeycomb lattice. Furthermore, we found a clear ×2.5 modulation in the topography, implying charge density wave or Moiré pattern originated from the interaction with the SiC substrate. Comparison with ARPES measurements provided us of further insight into the Fermi surface deduced from STS.

Operando NMR and XRD study of chemically synthesized LiCx oxidation in a dry room environment

DOE PAGES

Sacci, Robert L.; Gill, Lance W.; Hagaman, Edward W.; ...

2015-04-07

We test the stability of pre-lithiated graphite anodes for Li-ion batteries in a dry room battery processing room. The reaction between LiCx and laboratory air was followed using operando NMR and x-ray diffraction as these methods are sensitive to change in Li stoichiometry in graphite. There is minimal reactivity between LiC 6 and N 2, CO 2 or O 2; however, LiC 6 reacts with moisture to form lithium (hydr)oxide. The reaction rate follows zero-order kinetics with respects to intercalated lithium suggesting that lithium transport through the graphite is fast. The reaction mechanism occurs by sequential formation of higher stagesmore » LiC 12, then LiC 18, and then LiC 24 as the hydrolysis proceeds to the formation of Li xOH y and graphite end products. Slowing down the formation rate of the Li xOH y passivation layer stabilizes of the higher stages.« less

The 13C nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The (13)C NMR chemical shifts of graphite intercalation compounds were calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about -140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

Dynamics of graphite fiber intercalation: In situ resistivity measurements with a four point probe

NASA Technical Reports Server (NTRS)

Jaworske, D. A.

1984-01-01

The dynamics of ferric chloride intercalation of single graphite fibers were studied, in situ, using a four point dc bridge. Measurements before, during and after the intercalation showed that the intercalation occurred within minutes at 200 C. Changes in fiber resistivity after exposure to air suggested hydration of the graphite intercalation compound. Deintercalation of the ferric chloride was initiated at temperatures in excess of 400 C. cycling the intercalant into and out of the graphite fiber gave no improvements in fiber resistivity. The activation energy of the ferric chloride intercalation reaction was found to be 17 + or - 4 kcal/mol 1 consistent with the concept of a preliminary nucleation step in the intercalation reaction.

Influence of Li+ charge compensator ion on the energy transfer from Pr3 + to Gd3 + ions in Ca9Mg(PO4)6F2:Gd3 +, Pr3 +, Li+ phosphor

NASA Astrophysics Data System (ADS)

Tamboli, Sumedha; Dhoble, S. J.

2017-09-01

Phototherapy is a renowned treatment for curing skin diseases since ancient times. Phototherapeutic treatment for psoriasis and many other diseases require narrow band ultra violet-B (NB-UVB) light with peak intensity at 313 nm to be exposed to the affected part of body. In this paper, we report combustion synthesis of NB-UVB - 313 nm emitting Ca9Mg(PO4)6F2 phosphors doped with Gd3 +, Pr3 + and Li+ ions. The phase formation was confirmed by obtaining X-ray diffraction (XRD) pattern and morphology was studied with the Scanning electron microscopy (SEM) images. Photoluminescence (PL) emission spectra show intense narrow band emission at 313 nm under 274 nm excitation wavelengths. Emission intensity was enhanced when Ca9Mg(PO4)6F2 compound is co-doped with Pr3 + ions. Excitation spectra of Ca9Mg(PO4)6F2:Gd3 +, Pr3 + doped samples shows broad excitation in ultra violet C (UVC) region. Diffuse reflectance spectra (DRS), obtained by UV-visible spectrophotometer, measures the absorption properties of the material. By applying Kubelka Munk function on the diffuse reflectance spectra, band gap of the material is determined. PL decay curves were examined which indicates efficient energy transfer between Pr3 + and Gd3 + ions. Charge compensation effect was also studied by co-doping Li+ ion in host. Emission intensity was found to increase with the addition of charge compensator. The prepared phosphor has potential to convert UVC light into NB-UVB. The luminescence intensity of Gd3 + shows remarkable increase when it is sensitized with Pr3 +, and an addition of charge compensator in the form of Li+, show even better results. This phosphor surely has the potential to be used as phototherapy lamp phosphor.

Pillared graphite anodes for reversible sodiation.

PubMed

Zhang, Hanyang; Li, Zhifei; Xu, Wei; Chen, Yicong; Ji, Xiulei; Lerner, Michael M

2018-08-10

There has been a major effort recently to develop new rechargeable sodium-ion electrodes. In lithium ion batteries, LiC 6 forms from graphite and desolvated Li cations during the first charge. With sodium ions, graphite only shows a significant capacity when Na + intercalates as a solvated complex, resulting in ternary graphite intercalation compounds (GICs). Although this chemistry has been shown to be highly reversible and to support high rates in small test cells, these GICs can require >250% volume expansion and contraction during cycling. Here we demonstrate the first example of GICs that reversibly sodiate/desodiate without any significant volume change. These pillared GICs are obtained by electrochemical reduction of graphite in an ether/amine co-solvent electrolyte. The initial gallery expansion, 0.36 nm, is less than half of that in diglyme-based systems, and shows a similar capacity. Thermal analyses suggest the pillaring phenomenon arises from stronger co-intercalate interactions in the GIC galleries.

Durability of Intercalated Graphite Epoxy Composites in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Gaier, James R.; Davidson, Michelle L.; Shively, Rhonda

1996-01-01

The electrical conductivity of graphite epoxy composites can be substantially increased by intercalating (inserting guest atoms or molecules between the graphene planes) the graphite fibers before composite formation. The resulting high strength, low density, electrically conducting composites have been proposed for EMI shielding in spacecraft. Questions have been raised, however, about their durability in the space environment, especially with respect to outgassing of the intercalates, which are corrosive species such as bromine. To answer those concerns, six samples of bromine intercalated graphite epoxy composites were included in the third Evaluation of Oxygen Interaction with Materials (EOIM-3) experiment flown on the Space Shuttle Discovery (STS-46). Changes in electrical conductivity, optical reflectance, surface texture, and mass loss for SiO2 protected and unprotected samples were measured after being exposed to the LEO environment for 42 hours. SiO2 protected samples showed no degradation, verifying conventional protection strategies are applicable to bromine intercalated composites. The unprotected samples showed that bromine intercalation does not alter the degradation of graphite-epoxy composites. No bromine was detected to have been released by the fibers allaying fears that outgassing could be disruptive to the sensitive electronics the EMI shield is meant to protect.

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

1987-01-01

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Feasibility of intercalated graphite railgun armatures

NASA Technical Reports Server (NTRS)

Gaier, James R.; Gooden, Clarence E.; Yashan, Doreen; Naud, Steven

1990-01-01

Graphite intercalation compounds may provide an excellent material for the fabrication of electro-magnetic railgun armatures. As a pulse of power is fed into the armature the intercalate could be excited into the plasma state around the edges of the armature, while the bulk of the current would be carried through the graphite block. Such an armature would have the desirable characteristics of both diffuse plasma armatures and bulk conduction armatures. In addition, the highly anisotropic nature of these materials could enable the electrical and thermal conductivity to be tailored to meet the specific requirements of electromagnetic railgun armatures. Preliminary investigations were performed in an attempt to determine the feasibility of using graphite intercalation compounds as railgun armatures. Issues of fabrication, resistivity, stability, and electrical current spreading are addressed for the case of highly oriented pyrolytic graphite.

Purification process of natural graphite as anode for Li-ion batteries: chemical versus thermal

NASA Astrophysics Data System (ADS)

Zaghib, K.; Song, X.; Guerfi, A.; Rioux, R.; Kinoshita, K.

The intercalation of Li ions in natural graphite that was purified by chemical and thermal processes was investigated. A new chemical process was developed that involved a mixed aqueous solution containing 30% H 2SO 4 and 30% NH xF y heated to 90 °C. The results of this process are compared to those obtained by heating the natural graphite from 1500 to 2400 °C in an inert environment (thermal process). The first-cycle coulombic efficiency of the purified natural graphite obtained by the chemical process is 91 and 84% after the thermal process at 2400 °C. Grinding the natural graphite before or after purification had no significant effect on electrochemical performance at low currents. However, grinding to a very small particle size before purification permitted optimization of the size distribution of the particles, which gives rise to a more homogenous electrode. The impurities in the graphite play a role as microabrasion agents during grinding which enhances its hardness and improves its mechanical properties. Grinding also modifies the particle morphology from a 2- to a 3-D structure (similar in shape to a potato). This potato-shaped natural graphite shows high reversible capacity at high current densities (about 90% at 1 C rate). Our analysis suggests that thermal processing is considerably more expensive than the chemical process to obtain purified natural graphite.

Revealing the electronic structure of LiC 6 by soft X-ray spectroscopy

DOE PAGES

Zhang, L.; Li, X.; Augustsson, A.; ...

2017-03-09

The electronic structure of LiC 6 has been investigated in this paper by soft X-ray absorption and emission spectroscopies. The results reveal that upon full lithiation of graphite, the Li 2s electrons are transferred into the carbon π* states in a near rigid-band behavior, resulting in the increased density of states near E F and the shift of σ* states to lower energies. Finally, in addition, the resonant inelastic X-ray scattering spectra of LiC 6 do not show strong dispersive features as that of graphite, indicating that the crystal momentum is not conserved during the scattering process due to themore » delocalization of electrons in the intermediate state.« less

Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

NASA Astrophysics Data System (ADS)

Bhattacharya, Sandeep

This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt < 0.05 mVs-1 produced a tubular SEI that uniformly covered the graphite surface and prevented damage at 25°C. At 60°C, a high D Li+ formed a Li2CO3-enriched SEI and ensued a

Environmentally benign graphite intercalation compound composition for exfoliated graphite, flexible graphite, and nano-scaled graphene platelets

DOEpatents

Zhamu, Aruna; Jang, Bor Z.

2014-06-17

A carboxylic-intercalated graphite compound composition for the production of exfoliated graphite, flexible graphite, or nano-scaled graphene platelets. The composition comprises a layered graphite with interlayer spaces or interstices and a carboxylic acid residing in at least one of the interstices, wherein the composition is prepared by a chemical oxidation reaction which uses a combination of a carboxylic acid and hydrogen peroxide as an intercalate source. Alternatively, the composition may be prepared by an electrochemical reaction, which uses a carboxylic acid as both an electrolyte and an intercalate source. Exfoliation of the invented composition does not release undesirable chemical contaminants into air or drainage.

High-rate capability of three-dimensionally ordered macroporous T-Nb2O5 through Li+ intercalation pseudocapacitance

NASA Astrophysics Data System (ADS)

Lou, Shuaifeng; Cheng, Xinqun; Wang, Long; Gao, Jinlong; Li, Qin; Ma, Yulin; Gao, Yunzhi; Zuo, Pengjian; Du, Chunyu; Yin, Geping

2017-09-01

Orthorhombic Niobium oxide (T-Nb2O5) has been regarded as a promising anode material for high-rate lithium ion batteries (LIBs) due to its potential to operate at high rates with improved safety and high theoretical capacity of 200 mA h g-1. Herein, three-dimensionally ordered macroporous (3DOM) T-Nb2O5, with mesoporous hierarchical structure, was firstly prepared by a simple approach employing self-assembly polystyrene (PS) microspheres as hard templates. The obtained T-Nb2O5 anode material presents obvious and highly-efficiency pseudocapacitive Li+ intercalation behaviour, which plays a dominant role in the kinetics of electrode process. As a result, rapid Li+ intercalation/de-intercalation are achieved, leading to excellent rate capability and long cycle life. The 3DOM T-Nb2O5 shows a remarkable high capacity of 106 and 77 mA h g-1 at the rate of 20C and 50C. The work presented herein holds great promise for future design of material structure, and demonstrates the great potential of T-Nb2O5 as a practical high-rate anode material for LIBs.

A reactive force field study of Li/C systems for electrical energy storage

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

Raju, Muralikrishna; Ganesh, P.; Kent, Paul R. C.

Graphitic carbon is still the most ubiquitously used anode material in Li-ion batteries. In spite of its ubiquity, there are few theoretical studies that fully capture the energetics and kinetics of Li in graphite and related nanostructures at experimentally relevant length, time-scales, and Li-ion concentrations. In this paper, we describe the development and application of a ReaxFF reactive force field to describe Li interactions in perfect and defective carbon-based materials using atomistic simulations. We develop force field parameters for Li–C systems using van der Waals-corrected density functional theory (DFT). Grand canonical Monte Carlo simulations of Li intercalation in perfect graphitemore » with this new force field not only give a voltage profile in good agreement with known experimental and DFT results but also capture the in-plane Li ordering and interlayer separations for stage I and II compounds. In defective graphite, the ratio of Li/C (i.e., the capacitance increases and voltage shifts) both in proportion to the concentration of vacancy defects and metallic lithium is observed to explain the lithium plating seen in recent experiments. We also demonstrate the robustness of the force field by simulating model carbon nanostructures (i.e., both 0D and 1D structures) that can be potentially used as battery electrode materials. Whereas a 0D defective onion-like carbon facilitates fast charging/discharging rates by surface Li adsorption, a 1D defect-free carbon nanorod requires a critical density of Li for intercalation to occur at the edges. Our force field approach opens the opportunity for studying energetics and kinetics of perfect and defective Li/C structures containing thousands of atoms as a function of intercalation. As a result, this is a key step toward modeling of realistic carbon materials for energy applications.« less

A reactive force field study of Li/C systems for electrical energy storage

DOE PAGES

Raju, Muralikrishna; Ganesh, P.; Kent, Paul R. C.; ...

2015-04-02

Graphitic carbon is still the most ubiquitously used anode material in Li-ion batteries. In spite of its ubiquity, there are few theoretical studies that fully capture the energetics and kinetics of Li in graphite and related nanostructures at experimentally relevant length, time-scales, and Li-ion concentrations. In this paper, we describe the development and application of a ReaxFF reactive force field to describe Li interactions in perfect and defective carbon-based materials using atomistic simulations. We develop force field parameters for Li–C systems using van der Waals-corrected density functional theory (DFT). Grand canonical Monte Carlo simulations of Li intercalation in perfect graphitemore » with this new force field not only give a voltage profile in good agreement with known experimental and DFT results but also capture the in-plane Li ordering and interlayer separations for stage I and II compounds. In defective graphite, the ratio of Li/C (i.e., the capacitance increases and voltage shifts) both in proportion to the concentration of vacancy defects and metallic lithium is observed to explain the lithium plating seen in recent experiments. We also demonstrate the robustness of the force field by simulating model carbon nanostructures (i.e., both 0D and 1D structures) that can be potentially used as battery electrode materials. Whereas a 0D defective onion-like carbon facilitates fast charging/discharging rates by surface Li adsorption, a 1D defect-free carbon nanorod requires a critical density of Li for intercalation to occur at the edges. Our force field approach opens the opportunity for studying energetics and kinetics of perfect and defective Li/C structures containing thousands of atoms as a function of intercalation. As a result, this is a key step toward modeling of realistic carbon materials for energy applications.« less

Environmental stability of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, J. R.; Jaworske, D. A.

1985-01-01

Graphite fibers intercalated with bromine, iodine monochloride, ferric chloride, and cupric chloride were subjected to stability tests under four environments which are encountered by engineering materials in the aerospace industry: ambient laboratory conditions, as would be experienced during handling operations and terrestrial applications; high vacuum, as would be experienced in space applications; high humidity, as would be experienced in marine applications; and high temperature, as would be experienced in some processing steps and applications. Monitoring the resistance of the fibers at ambient laboratory conditions revealed that only the ferric chloride intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were unstable, due to absorption of water from the air. All four types of intercalated fibers were stable for long periods under high vacuum. Ferric chloride, cupric chloride, and iodine monochloride intercalated fibers were sensitive to high humidity conditions. All intercalated fibers began to degrade above 250 C. The order of their thermal stability, from lowest to highest, was cupric chloride, iodine monochloride, bromine, and ferric chloride. Of the four types of intercalated fibers tested, the bromine intercalated fibers appear to have the most potential for application, based on environmental stability.

Optically pumped cerium-doped LiSrAlF.sub.6 and LiCaAlF.sub.6

DOEpatents

Marshall, Christopher D.; Payne, Stephen A.; Krupke, William F.

1996-01-01

Ce.sup.3+ -doped LiSrAlF.sub.6 crystals are pumped by ultraviolet light which is polarized along the c axis of the crystals to effectively energize the laser system. In one embodiment, the polarized fourth harmonic light output from a conventional Nd:YAG laser operating at 266 nm is arranged to pump Ce:LiSrAlF.sub.6 with the pump light polarized along the c axis of the crystal. The Ce:LiSrAlF.sub.6 crystal may be placed in a laser cavity for generating tunable coherent ultraviolet radiation in the range of 280-320 nm. Additionally, Ce-doped crystals possessing the LiSrAlF.sub.6 type of chemical formula, e.g. Ce-doped LiCaAlF.sub.6 and LiSrGaF.sub.6, can be used. Alternative pump sources include an ultraviolet-capable krypton or argon laser, or ultraviolet emitting flashlamps. The polarization of the pump light will impact operation. The laser system will operate efficiently when light in the 280-320 nm gain region is injected or recirculated in the system such that the beam is also polarized along the c axis of the crystal. The Ce:LiSrAlF.sub.6 laser system can be configured to generate ultrashort pulses, and it may be used to pump other devices, such as an optical parametric oscillator.

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

PubMed

Dinkelacker, Franz; Marzak, Philipp; Yun, Jeongsik; Liang, Yunchang; Bandarenka, Aliaksandr S

2018-04-25

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li + but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

Investigation on LiBH4-CaH2 composite and its potential for thermal energy storage.

PubMed

Li, Yang; Li, Ping; Qu, Xuanhui

2017-01-31

The LiBH 4 /CaH 2 composite are firstly studied as Concentrating Solar Power Thermal Storage Material. The LiBH 4 /CaH 2 composite according to the stoichiometric ratio are synthesized by high-energy ball milling method. The kinetics, thermodynamics and cycling stability of LiBH 4 /CaH 2 composite are investigated by XRD (X-ray diffraction), DSC (Differential scanning calorimeter) and TEM (Transmission electron microscope). The reaction enthalpy of LiBH 4 /CaH 2 composite is almost 60 kJ/mol H 2 and equilibrium pressure is 0.482 MPa at 450 °C. The thermal storage density of LiBH 4 /CaH 2 composite is 3504.6 kJ/kg. XRD results show that the main phase after dehydrogenation is LiH and CaB 6 . The existence of TiCl 3 and NbF 5 can effectively enhance the cycling perfomance of LiBH 4 /CaH 2 composite, with 6-7 wt% hydrogen capacity after 10 cycles. The high thermal storage density, high working temperature and low equilibrium pressure make LiBH 4 /CaH 2 composite a potential thermal storage material.

Preparation, quantitative surface analysis, intercalation characteristics and industrial implications of low temperature expandable graphite

NASA Astrophysics Data System (ADS)

Peng, Tiefeng; Liu, Bin; Gao, Xuechao; Luo, Liqun; Sun, Hongjuan

2018-06-01

Expandable graphite is widely used as a new functional carbon material, especially as fire-retardant; however, its practical application is limited due to the high expansion temperature. In this work, preparation process of low temperature and highly expandable graphite was studied, using natural flake graphite as raw material and KMnO4/HClO4/NH4NO3 as oxidative intercalations. The structure, morphology, functional groups and thermal properties were characterized during expanding process by Fourier transform infrared spectroscopy (FTIR), Raman spectra, thermo-gravimetry differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM). The analysis showed that by oxidation intercalation, some oxygen-containing groups were grafted on the edge and within the graphite layer. The intercalation reagent entered the graphite layer to increase the interlayer spacing. After expansion, the original flaky expandable graphite was completely transformed into worm-like expanded graphite. The order of graphite intercalation compounds (GICs) was proposed and determined to be 3 for the prepared expandable graphite, based on quantitative XRD peak analysis. Meanwhile, the detailed intercalation mechanisms were also proposed. The comprehensive investigation paved a benchmark for the industrial application of such sulfur-free expanded graphite.

In Situ Raman Microscopy of a Single Graphite Microflake Electrode in a Li(+)-containing Electrolyte

NASA Technical Reports Server (NTRS)

Shi, Qing-Fang; Dokko, Kaoru; Scherson, Daniel A.

2003-01-01

Highly detailed Raman spectra from a single KS-44 graphite microflake electrode as a function of the applied potential have been collected in situ using a Raman microscope and a sealed spectroelectrochemical cell isolated from the laboratory environment. Correlations were found between the Raman spectral features and the various Li(+) intercalation stages while recording in real time Raman spectra during a linear potential scan from 0.7 down ca. 0.0V vs Li/Li(+) at a rate of 0.1 mV/s in a 1M LiClO4 solution in a 1:l (by volume) ethylene carbonate (EC):diethyl carbonate (DEC) mixture. In particular, clearly defined isosbestic points were observed for data collected in the potential range where the transition between dilute phase 1 and phase 4 of lithiated graphite is known to occur, i.e. 0.157 < E < 0.215 vs Li/Li(+). Statistical analysis of the spectroscopic data within this region made it possible to determine independently the fraction of each of the two phases present as a function of potential without relying on coulometric information and then predict, based on the proposed stoichiometry for the transition, a spectrally-derived voltammetric feature.

Optically pumped cerium-doped LiSrAlF{sub 6} and LiCaAlF{sub 6}

DOEpatents

Marshall, C.D.; Payne, S.A.; Krupke, W.F.

1996-05-14

Ce{sup 3+}-doped LiSrAlF{sub 6} crystals are pumped by ultraviolet light which is polarized along the c axis of the crystals to effectively energize the laser system. In one embodiment, the polarized fourth harmonic light output from a conventional Nd:YAG laser operating at 266 nm is arranged to pump Ce:LiSrAlF{sub 6} with the pump light polarized along the c axis of the crystal. The Ce:LiSrAlF{sub 6} crystal may be placed in a laser cavity for generating tunable coherent ultraviolet radiation in the range of 280-320 nm. Additionally, Ce-doped crystals possessing the LiSrAlF{sub 6} type of chemical formula, e.g. Ce-doped LiCaAlF{sub 6} and LiSrGaF{sub 6}, can be used. Alternative pump sources include an ultraviolet-capable krypton or argon laser, or ultraviolet emitting flashlamps. The polarization of the pump light will impact operation. The laser system will operate efficiently when light in the 280-320 nm gain region is injected or recirculated in the system such that the beam is also polarized along the c axis of the crystal. The Ce:LiSrAlF{sub 6} laser system can be configured to generate ultrashort pulses, and it may be used to pump other devices, such as an optical parametric oscillator. 10 figs.

Superconductivity at 7.4 K in few layer graphene by Li-intercalation.

PubMed

Tiwari, Anand P; Shin, Soohyeon; Hwang, Eunhee; Jung, Soon-Gil; Park, Tuson; Lee, Hyoyoung

2017-11-08

Superconductivity in graphene has been highly sought after for its promise in various device applications and for general scientific interest. Ironically, the simple electronic structure of graphene, which is responsible for novel quantum phenomena, hinders the emergence of superconductivity. Theory predicts that doping the surface of the graphene effectively alters the electronic structure, thus promoting propensity towards Cooper pair instability (Profeta et al (2012) Nat. Phys. 8 131-4; Nandkishore et al (2012) Nat. Phys. 8 158-63) [1, 2]. Here we report the emergence of superconductivity at 7.4 K in Li-intercalated few-layer-graphene (FLG). The absence of superconductivity in 3D Li-doped graphite underlines that superconductivity in Li-FLG arises from the novel electronic properties of the 2D graphene layer. These results are expected to guide future research on graphene-based superconductivity, both in theory and experiments. In addition, easy control of the Li-doping process holds promise for various device applications.

High Voltage LiNi 0.5 Mn 0.3 Co 0.2 O 2 /Graphite Cell Cycled at 4.6 V with a FEC/HFDEC-Based Electrolyte

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

He, Meinan; Su, Chi-Cheung; Feng, Zhenxing

2017-04-26

A high voltage LiNi0.5Mn0.3Co0.2O2/graphite cell with a fluorinated electrolyte formulation 1.0 m LiPF6 fluoroethylene carbonate/bis(2,2,2-trifluoroethyl) carbonate is reported and its electrochemical performance is evaluated at cell voltage of 4.6 V. Comparing with its nonfluorinated electrolyte counterpart, the reported fluorinated one shows much improved Coulombic efficiency and capacity retention when a higher cut-off voltage (4.6 V) is applied. Scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy data clearly demonstrate the superior oxidative stability of the new electrolyte. The structural stability of the bulk cathode materials cycled with different electrolytes is extensively studied by X-ray absorption near edge structure andmore » X-ray diffraction.« less

Rechargeable LiNiO2/carbon cells

NASA Astrophysics Data System (ADS)

Dahn, J. R.; von Sacken, U.; Juzkow, M. W.; Al-Janaby, H.

1991-08-01

Rechargeable cells can be made using two different intercalation compounds, in which the chemical potential of the intercalant differs by several eV, for the electrodes. The factors that play a role in the selection of appropriate lithium intercalation compounds for such cells are discussed. For the ease of cell assembly, the cathode should be stable in air when it is fully intercalated, like LiNiO2. For the anode, the chemical potential of the intercalated Li should be close to that of Li metal, like it is in Li(x)C6. The intercalation of Li in LiNiO2 is discussed, and then in petroleum coke. Then, it is shown that LiNiO2/coke cells have high energy density, long cycle life, excellent high-temperature performance, low self-discharge rates, can be repeatedly discharged to zero volts without damage, and are easily fabricated. It is considered that this type of cell shows far more promise for widespread applications than traditional secondary Li cells using metallic Li anodes.

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra.

PubMed

Marashdeh, Ali; Frankcombe, Terry J

2008-06-21

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra

NASA Astrophysics Data System (ADS)

Marashdeh, Ali; Frankcombe, Terry J.

2008-06-01

The dehydrogenation enthalpies of Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH4)2 is exothermic, indicating a metastable hydride. Calculations for CaAlH5 including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH4 with CaH2 is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH4)2 and CaAlH5 calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH5 is presented in the more useful standard setting of P21/c symmetry and the phonon density of states of CaAlH5, significantly different to other common complex metal hydrides, is rationalized.

First-principles theory of cation- and intercalation-ordering in Li_xCoO_2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

1998-03-01

Using a combination of first-principles total energies, a cluster expansion technique, and Monte Carlo simulations, we present a first-principles theory which can predict both cation- and intercalation-ordering patterns at both zero and finite temperatures, and can provide first-principles predictions of battery voltages of Li_xCoO_2/Li cells. The classes of ordering problems that we study are the following: (i) The LiMO2 oxides (M=3d metal) form a series of structures based on an octahedrally-coordinated network with anions (O) on one fcc sublattice and cations (Li and M) on the other, leading to Li/Co ordering in LiCoO2 (x=1). We find the ground state is the CuPt or (111)-layered cation arrangment, in agreement with the observed structure. (ii) In battery applications, Li is (de)intercalated from the compound, creating a vacancy (denoted Box) that can be positioned in different lattice locations; Thus, Box/Co ordering in BoxCoO2 (x=0) is also of interest. We find the ground state for BoxCoO2 is also a (111)-layered structure, although a different stacking sequence (AAA) of close-packed layers is preferred. (iii) The vacancies left behind by Li extraction can form ordered vacancy compounds in partially de-lithiated Li_xCoO_2, leading to a Box/Li ordering problem (0<=x<=1). Our calculations agree with the observed voltage profiles in these systems, and predict the existence of new intercalation-ordered compounds. Supported by BES/OER/DMS under contract DE-AC36-83CH10093.

The staging mechanism of AlCl4 intercalation in a graphite electrode for an aluminium-ion battery.

PubMed

Bhauriyal, Preeti; Mahata, Arup; Pathak, Biswarup

2017-03-15

Identifying a suitable electrode material with desirable electrochemical properties remains a primary challenge for rechargeable Al-ion batteries. Recently an ultrafast rechargeable Al-ion battery was reported with high charge/discharge rate, (relatively) high discharge voltage and high capacity that uses a graphite-based cathode. Using calculations from first-principles, we have investigated the staging mechanism of AlCl 4 intercalation into bulk graphite and evaluated the stability, specific capacity and voltage profile of AlCl 4 intercalated compounds. Ab initio molecular dynamics is performed to investigate the thermal stability of AlCl 4 intercalated graphite structures. Our voltage profiles show that the first AlCl 4 intercalation step could be a more sluggish step than the successive intercalation steps. However, the diffusion of AlCl 4 is very fast in the expanded graphite host layers with a diffusion barrier of ∼0.01 eV, which justifies the ultrafast charging rate of a graphite based Al-ion battery. And such an AlCl 4 intercalated battery provides an average voltage of 2.01-2.3 V with a maximum specific capacity of 69.62 mA h g -1 , which is excellent for anion intercalated batteries. Our density of states and Bader charge analysis shows that the AlCl 4 intercalation into the bulk graphite is a charging process. Hence, we believe that our present study will be helpful in understanding the staging mechanism of AlCl 4 intercalation into graphite-like layered electrodes for Al-ion batteries, thus encouraging further experimental work.

Metallization and superconductivity in Ca-intercalated bilayer MoS2

NASA Astrophysics Data System (ADS)

Szczȱśniak, R.; Durajski, A. P.; Jarosik, M. W.

2017-12-01

A two-dimensional molybdenum disulfide (MoS2) has attracted significant interest recently due to its outstanding physical, chemical and optoelectronic properties. In this paper, using the first-principles calculations, the dynamical stability, electronic structure and superconducting properties of Ca-intercalated bilayer MoS2 are investigated. The calculated electron-phonon coupling constant implies that the stable form of investigated system is a strong-coupling superconductor (λ = 1.05) with a low value of critical temperature (TC = 13.3 K). Moreover, results obtained within the framework of the isotropic Migdal-Eliashberg formalism proved that Ca-intercalated bilayer MoS2 exhibits behavior that goes beyond the scope of the conventional BCS theory.

Comparison of fluoride intercalation/de-intercalation processes on graphite electrodes in aqueous and aqueous methanolic HF media

NASA Astrophysics Data System (ADS)

Noel, M.; Santhanam, R.; Francisca Flora, M.

The solvent can play a major role in the intercalation/de-intercalation process and the stability of graphite substrates towards this process. This fact is established in the present work that involves fluoride intercalation/de-intercatlation on graphite electrodes in aqueous and aqueous methanolic HF solutions where the HF concentration is varied between 1.0 and 18.0 M. In addition to cyclic voltammetry and potentiostatic polarization, open-circuit potential decay measurements, scanning electron microscopy and X-ray diffraction measurements have been employed. In general, addition of methanol and increasing concentration of HF raise the overall intercalation/de-intercalation efficiency. Methanol is adsorbed preferentially on the graphite lattice and, hence, suppresses both oxygen evolution and the formation of passive graphite oxides. In 15.0 M HF, the optimum methanol concentration is 5 vol.%. This suggests that, in addition to the adsorption effect, there is some weakening of the structured water molecules that facilitates the solvated fluoride ions for efficient intercalation.

Enhanced Thermal Diffusion of Li in Graphite by Alternating Vertical Electric Field: A Hybrid Quantum-Classical Simulation Study

NASA Astrophysics Data System (ADS)

Ohba, Nobuko; Ogata, Shuji; Tamura, Tomoyuki; Kobayashi, Ryo; Yamakawa, Shunsuke; Asahi, Ryoji

2012-02-01

Enhancing the diffusivity of the Li ion in a Li-graphite intercalation compound that has been used as a negative electrode in the Li-ion rechargeable battery, is important in improving both the recharging speed and power of the battery. In the compound, the Li ion creates a long-range stress field around itself by expanding the interlayer spacing of graphite. We advance the hybrid quantum-classical simulation code to include the external electric field in addition to the long-range stress field by first-principles simulation. In the hybrid code, the quantum region selected adaptively around the Li ion is treated using the real-space density-functional theory for electrons. The rest of the system is described with an empirical interatomic potential that includes the term relating to the dispersion force between the C atoms in different layers. Hybrid simulation runs for Li dynamics in graphite are performed at 423 K under various settings of the amplitude and frequency of alternating electric fields perpendicular to C-layers. We find that the in-plane diffusivity of the Li ion is enhanced significantly by the electric field if the amplitude is larger than 0.2 V/Å within its order and the frequency is as high as 1.7 THz. The microscopic mechanisms of the enhancement are explained.

High-Temperature Intercalated Graphite Fiber Conductors Fabricated

NASA Technical Reports Server (NTRS)

Gaier, James R.

2002-01-01

Composites of intercalated graphite fibers show promise to significantly reduce the weight of electromagnetic interference shielding in spacecraft and aircraft. Bromine intercalated pitch-based fibers have been among the most heavily studied systems because of their attractive electrical and thermal conductivities and their stability over a wide range of environmental conditions. Previous studies found that the resistivity of bromineintercalated graphite fibers began to increase when the fibers were exposed to temperatures in excess of about 200 C in air for long periods of time. If the temperature was as high as 450 C, the resistivity increased dramatically within a few hours. It remained unclear, however, whether the increase was due to deintercalation of the bromine or to air oxidation of the fibers. Studies were initially directed toward determining the temperature at which bromine would deintercalate from the fibers, and perhaps become a hazard to both personnel and equipment. So the mass of bromine-intercalated graphite fibers was carefully monitored as it was heated in an inert atmosphere, since the fibers are known to oxidize at a lower temperature than they deintercalate. What was found was that the fibers, which are about 18-wt% bromine, did not lose any appreciable mass even at temperatures approaching 1000 C. X-ray diffraction studies showed that there were also no changes in the overall structure of the compound. Resistivity measurements indicated that there is some slight degradation in the electronic structure, in that the resistivity increased by a few percent. Overall, the results show that these materials may be suitable for applications at temperatures at least this high, provided oxygen is excluded. This may enable their use in carbon-ceramic, and perhaps even carbon-carbon composites.

Investigation of Glutaric Anhydride as an Electrolyte Additive for Graphite/LiNi 0.5 Mn 0.3 Co 0.2 O 2 Full Cells

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

Peebles, Cameron; He, Meinan; Feng, Zhenxing

The effects of glutaric anhydride (GA) as an electrolyte additive for graphite/LiNi0.5Mn0.3Co0.2O2 full cells operating between 3.0-4.4 V were investigated. Linear scan voltammetry (LSV) revealed that GA preferentially oxidized prior to the carbonate-based electrolyte while Li/graphite half cells revealed that GA can suppress electrolyte decomposition on the graphite electrode giving rise to the bifunctional nature of this additive. The addition of both 0.5 and 1.0 wt% of GA into the carbonate-based electrolyte resulted in superior cycling performance compared to the baseline electrolyte as demonstrated by the slight increase in initial capacities and significant increases in capacity retention over 117 cyclesmore » at C/3. Electrochemical impedance spectroscopy (EIS) showed that while the overall impedance of the GA containing cells was higher than the cells with the baseline electrolyte the change in impedance between post-formation and post-cycling was smallest for the cells containing GA. Additionally, X-ray photoelectron spectroscopy (XPS) analysis confirmed that GA decomposed on the cathode surface leading to an increase in oxygen-containing species, a decrease in LiF species and a simultaneous increase in LixPOyFz species. (C) 2016 The Electrochemical Society. All rights reserved.« less

Fundamental Electronic Properties of Donor-Type Graphite Intercalated Compounds.

DTIC Science & Technology

1984-08-01

charge distribution for 2nd and 3rd stage Li-graphite. Our results showed that, in fact , the major part of the transferred charge is concentrated in the...the fact "melting" would be a continuous loss of c-axis corre- that the same exponent fits the data in the range latlons, which would broaden the (100...all cases. The fact that the I! sublattice is not entirely decoupled from closest approach to agreement is between the RS data the graphite network at

LiCaFeF6: A zero-strain cathode material for use in Li-ion batteries

NASA Astrophysics Data System (ADS)

de Biasi, Lea; Lieser, Georg; Dräger, Christoph; Indris, Sylvio; Rana, Jatinkumar; Schumacher, Gerhard; Mönig, Reiner; Ehrenberg, Helmut; Binder, Joachim R.; Geßwein, Holger

2017-09-01

A new zero-strain LiCaFeF6 cathode material for reversible insertion and extraction of lithium ions is presented. LiCaFeF6 is synthesized by a solid-state reaction and processed to a conductive electrode composite via high-energy ball-milling. In the first cycle, a discharge capacity of 112 mAh g-1 is achieved in the voltage range from 2.0 V to 4.5 V. The electrochemically active redox couple is Fe3+/Fe2+ as confirmed by Mössbauer spectroscopy and X-ray absorption spectroscopy. The compound has a trigonal colquiriite-type crystal structure (space group P 3 bar 1 c). By means of in situ and ex situ XRD as well as X-ray absorption fine structure spectroscopy a reversible response to Li uptake/release is found. For an uptake of 0.8 mol Li per formula unit only minimal changes occur in the lattice parameters causing a total change in unit cell volume of less than 0.5%. The spatial distribution of cations in the crystal structure as well as the linkage between their corresponding fluorine octahedra is responsible for this very small structural response. With its zero-strain behaviour this material is expected to exhibit only negligible mechanical degradation. It may be used as a cathode material in future lithium-ion batteries with strongly improved safety and cycle life.

Graphite|LiFePO4 lithium-ion battery working at the heat engine coolant temperature

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Kurc, Beata; Swiderska-Mocek, Agnieszka; Kusa, Natalia

2014-11-01

Electrochemical properties of the graphite anode and the LiFePO4 cathode, working together with the 1 M LiPF6 in TMS (sulpholane) at 90 °C have been studied. The general aim of the investigation was to demonstrate a potential application for a Li-ion cell working in the cooling system of a car heat engine (90 °C). Electrodes were characterized with the use of electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) as well as galvanostatic charging/discharging tests. SEM images of both electrodes after charging/discharging processes were covered with a film (electrochemical SEI formation). The charge transfer resistance at 90 °C, Rct, of the C6Li|Li+ anode and the LiFePO4 cathode was 24 Ω and 110 Ω, respectively. Reversible capacity of the LiC6 anode after 10-20 cycles, at a low current rate was close to the theoretical value of 370 mAh g-1 however an increasing current rate decreased to ca. 200 mAh g-1 (for 1C). The reversibility of the process was close to 95%. The capacity of the LiFePO4 cathode was ca. 150 mAh g-1, almost independent of the current rate and close to the theoretical value of 170 mAh g-1.

Superconductivity under high pressure in the binary compound CaLi2

NASA Astrophysics Data System (ADS)

Debessai, M.; Matsuoka, T.; Hamlin, J. J.; Gangopadhyay, A. K.; Schilling, J. S.; Shimizu, K.; Ohishi, Y.

2008-12-01

Feng predicted for CaLi2 highly anomalous properties with possible superconductivity under very high pressures, including for the hcp polymorph a significant lattice bifurcation at pressures above 47 GPa. More recently, however, Feng suggested that for pressures exceeding 20 GPa CaLi2 may dissociate into elemental Ca and Li. Here we present for hcp CaLi2 measurements of the electrical resistivity and ac susceptibility to low temperatures under pressures as high as 81 GPa. Pressure-induced superconductivity is observed in the pressure range of 11-81 GPa, with Tc reaching values as high as 13 K. X-ray diffraction studies to 54 GPa at 150 K reveal that hcp CaLi2 undergoes a structural phase transition above 23 GPa to orthorhombic but does not dissociate into elemental Ca and Li. In the hcp phase a fit of the equation of state with the Murnaghan equation yields the bulk modulus Bo=15(2)GPa and dBo/dP=3.2(6) .

1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether as a co-solvent for high voltage LiNi1/3Co1/3Mn1/3O2/graphite cells

NASA Astrophysics Data System (ADS)

Wang, Chengyun; Zuo, Xiaoxi; Zhao, Minkai; Xiao, Xin; Yu, Le; Nan, Junmin

2016-03-01

1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether (F-EAE) mixed with ethylene carbonate (EC), diethyl carbonate (DEC), and lithium hexafluorophosphate (LiPF6) is evaluated as a co-solvent high-potential electrolyte of LiNi1/3Co1/3Mn1/3O2/graphite batteries. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) indicate that the EC/DEC-based electrolyte with F-EAE possesses a high oxidation potential (>5.2 V vs. Li/Li+) and excellent film-forming characteristics. With 40 wt% F-EAE in the electrolyte, the capacity retention of the LiNi1/3Co1/3Mn1/3O2/graphite pouch cells that are cycled between 3.0 and 4.5 V is significantly improved from 28.8% to 86.8% after 100 cycles. In addition, electrochemical impedance spectroscopy (EIS) of three-electrode pouch cells, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) are used to characterize the effects of F-EAE on the enhanced capacity retention. It is demonstrated that F-EAE facilitates the formation of a stable surface electrolyte interface (SEI) layer with low impedance on the anode and effectively suppresses an increase in the charge-transfer resistance on the cathode. These results suggest that F-EAE can serve as an alternative electrolyte solvent for 4.5 V high voltage rechargeable lithium-ion batteries.

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

High performance 1.2 Ah Si-alloy/Graphite|LiNi0.5Mn0.3Co0.2O2 prototype Li-ion battery

NASA Astrophysics Data System (ADS)

Marinaro, Mario; Yoon, Dong-hwan; Gabrielli, Giulio; Stegmaier, Petra; Figgemeier, Egbert; Spurk, Paul C.; Nelis, Daniël; Schmidt, Gregory; Chauveau, Jerome; Axmann, Peter; Wohlfahrt-Mehrens, Margret

2017-07-01

The study reports on realization and electrochemical testing of prototype Si-alloy/Graphite|LiNi0.5Mn0.3Co0.2O2 batteries. Water soluble polyacrylic acid (PAA), used as the only binder at the anode side, demonstrates excellent dispersant and binding properties. Sedimentation tests and rheological measurements show remarkable stability and mostly a thinning behavior of the non-Newtonian type of slurry. The cathode is processed in N-Methylpyrrolidone based slurry using polyvinylidene fluoride (PVDF) as the binding agent. The electronic conductivities of the manufactured Si-alloy/Graphite and LiNi0.5Mn0.3Co0.2O2 electrodes are evaluated. Furthermore, the cathode and anode electrochemical behavior is initially studied in half-cells, and subsequently in full Li-ion stacked prototype soft pouch-cells (1.22 Ah). It is demonstrated that the manufactured prototype cells can sustain about 290 charge/discharge galvanostatic cycles before the retained capacity drops below 80%. Cell aging is monitored using Electrochemical Impedance Spectroscopy (EIS), whereas post-mortem SEM analysis of electrodes cross-section is used to shed light on the causes of performance degradation of the cells.

Lithiation-induced zinc clustering of Zn 3, Zn 12, and Zn 18 units in Zintl-like Ca ~30Li 3+xZn 60-x (x=0.44-1.38)

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

Lin, Qisheng

2014-11-14

Zinc clusters are not common for binary intermetallics with relatively low zinc content, but this work shows that zinc clustering can be triggered by lithiation, as exemplified by Ca ~30Li 3+xZn 60-x, P6/mmm, Z = 1, which can be directly converted from CaZn 2. Two end members of the solid solution (x = 0.44 and 1.38) were established and structurally characterized by single-crystal X-ray diffraction analyses: Ca 30Li 3.44(6)Zn59.56(6), a = 15.4651(9) Å, c = 9.3898(3) Å; Ca 30.45(2)Li 4.38(6)Zn 58.62(6), a = 15.524(3) Å, c = 9.413(2) Å. The structures of Ca ~30Li 3+xZn 60-x feature a condensed anionicmore » network of Zn3 triangles, lithium-centered Zn12 icosahedra, and arachno-(Zn,Li)18 tubular clusters that are surrounded respectively by Ca 14, Ca 20, and Ca 30 polyhedra. These polyhedra share faces and form a clathrate-like cationic framework. The specific occupation of lithium in the structure is consistent with theoretical “coloring” analyses. Analysis by the linear muffin-tin orbital (LMTO) method within the atomic sphere approximation reveals that Ca ~30Li 3+xZn 60-x is a metallic, Zintl-like phase with an open-shell electronic structure. The contribution of Ca–Zn polar covalent interactions is about 41%.« less

An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite compounds.

PubMed

Cheng, Hansong; Sha, Xianwei; Chen, Liang; Cooper, Alan C; Foo, Maw-Lin; Lau, Garret C; Bailey, Wade H; Pez, Guido P

2009-12-16

We present a combined theoretical and experimental study on H(2) physisorption in partially fluorinated graphite. This material, first predicted computationally using ab initio molecular dynamics simulation and subsequently synthesized and characterized experimentally, represents a novel class of "acceptor type" graphite intercalated compounds that exhibit significantly higher isosteric heat of adsorption for H(2) at near ambient temperatures than previously demonstrated for commonly available porous carbon-based materials. The unusually strong interaction arises from the semi-ionic nature of the C-F bonds. Although a high H(2) storage capacity (>4 wt %) at room temperature is predicted not to be feasible due to the low heat of adsorption, enhanced storage properties can be envisaged by doping the graphitic host with appropriate species to promote higher levels of charge transfer from graphene to F(-) anions.

Luminescence study of Dy or Ce activated LiCaBO3 phosphor for γ-ray and C5+ ion beam irradiation.

PubMed

Oza, Abha H; Dhoble, N S; Lochab, S P; Dhoble, S J

2015-11-01

The photoluminescence and thermoluminescence characteristics of rare earths (Dy or Ce) activated LiCaBO3 phosphors have been studied. Phosphors were synthesized by modified solid state synthesis. The phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and thermoluminescence (TL) for structural, morphological and luminescence studies. Dy(3+) activated LiCaBO3 shows emission at 486 and 577 nm due to (4) F9/2 →(6) H15/2 and (4) F9/2 → (6) H13/2 transition, respectively, whereas the PL emission spectra of Ce(3+) activated LiCaBO3 phosphor shows a broad band peaking at 432 nm, which is due to the transition from 5d level to the ground state of the Ce(3+) ion. The thermoluminescence study was also carried out for both these phosphors for γ-ray irradiation and carbon beam irradiation. Linearity was studied for a 0.4-3.1 Rad dose γ-rays. Linear behaviour over this dose range was observed. Gamma ray-irradiated phosphors were shown to be negligible fading upon storage. All the samples were also studied for 75 MeV C(5+) ion beam exposure in the range of 3.75 × 10(12) - 7.5 × 10(13) ion cm(-2) fluence. In addition to this, trapping parameters of all the samples were also calculated using Chen's peak shape method. Copyright © 2015 John Wiley & Sons, Ltd.

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

NASA Astrophysics Data System (ADS)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2009-06-01

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated ( 6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated ( 6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

Superconductivity in graphite intercalation compounds

DOE PAGES

Smith, Robert P.; Weller, Thomas E.; Howard, Christopher A.; ...

2015-02-26

This study examines the field of superconductivity in the class of materials known as graphite intercalation compounds which has a history dating back to the 1960s. This paper recontextualizes the field in light of the discovery of superconductivity in CaC₆ and YbC₆ in 2005. In what follows, we outline the crystal structure and electronic structure of these and related compounds. We go on to experiments addressing the superconducting energy gap, lattice dynamics, pressure dependence, and how this relates to theoretical studies. The bulk of the evidence strongly supports a BCS superconducting state. However, important questions remain regarding which electronic statesmore » and phonon modes are most important for superconductivity and whether current theoretical techniques can fully describe the dependence of the superconducting transition temperature on pressure and chemical composition.« less

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

PubMed

Seiler, Steffen; Halbig, Christian E; Grote, Fabian; Rietsch, Philipp; Börrnert, Felix; Kaiser, Ute; Meyer, Bernd; Eigler, Siegfried

2018-02-26

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

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.

Superconducting Continuous Graphene Fibers via Calcium Intercalation.

PubMed

Liu, Yingjun; Liang, Hui; Xu, Zhen; Xi, Jiabin; Chen, Genfu; Gao, Weiwei; Xue, Mianqi; Gao, Chao

2017-04-25

Superconductors are important materials in the field of low-temperature magnet applications and long-distance electrical power transmission systems. Besides metal-based superconducting materials, carbon-based superconductors have attracted considerable attention in recent years. Up to now, five allotropes of carbon, including diamond, graphite, C 60 , CNTs, and graphene, have been reported to show superconducting behavior. However, most of the carbon-based superconductors are limited to small size and discontinuous phases, which inevitably hinders further application in macroscopic form. Therefore, it raises a question of whether continuously carbon-based superconducting wires could be accessed, which is of vital importance from viewpoints of fundamental research and practical application. Here, inspired by superconducting graphene, we successfully fabricated flexible graphene-based superconducting fibers via a well-established calcium (Ca) intercalation strategy. The resultant Ca-intercalated graphene fiber (Ca-GF) shows a superconducting transition at ∼11 K, which is almost 2 orders of magnitude higher than that of early reported alkali metal intercalated graphite and comparable to that of commercial superconducting NbTi wire. The combination of lightness and easy scalability makes Ca-GF highly promising as a lightweight superconducting wire.

A comparison of the transport properties of lithium-stuffed garnets and the conventional phases Li 3Ln3Te 2O 12

NASA Astrophysics Data System (ADS)

Cussen, Edmund J.; Yip, Thomas W. S.; O'Neill, Gemma; O'Callaghan, Michael P.

2011-02-01

The structures of new phases Li 6CaLa 2Sb 2O 12 and Li 6.4Ca 1.4La 2Sb 2O 12 have been characterised using neutron powder diffraction. Rietveld analyses show that both compounds crystallise in the space group la3¯ d and contain the lithium cations in a complex arrangement with occupational disorder across oxide tetrahedra and distorted oxide octahedra, with considerable positional disorder in the latter. Variable temperature neutron diffraction experiments on Li 6.4Ca 1.4La 2Sb 2O 12 show the structure is largely invariant with only a small variation in the lithium distribution as a function of temperature. Impedance spectroscopy measurements show that the total conductivity of Li 6CaLa 2Sb 2O 12 is several orders of magnitude smaller than related lithium-stuffed garnets with σ=10 -7 S cm -1 at 95 °C and an activation energy of 0.82(3) eV. The transport properties of the conventional garnets Li 3Gd 3Te 2O 12, Li 3Tb 3Te 2O 12, Li 3Er 3Te 2O 12 and Li 3Lu 3Te 2O 12 have been evaluated and consistently show much lower values of conductivity, σ≤4.4×10 -6 S cm -1 at 285 °C and activation energies in the range 0.77(4)≤ Ea/eV≤1.21(3).

Effect of Acetylene Black Content to Half Cells Li-ion Battery Performance Based on Li4Ti5O12 using Li2CO3 as Lithium Ion Source with Hydrothermal Mechanochemical Process

NASA Astrophysics Data System (ADS)

Priyono, B.; Faizah; Syahrial, A. Z.; Subhan, A.

2017-07-01

Lithium titanate (Li4Ti5O12)/LTO is a promising candidate to be used as anode electrode in Li-ion battery, to replace graphite in Li-ion battery application. Crystal structure of lithium titanate/LTO is more stable or undergoes less strain than graphite during intercalation and de-intercalation process Li+ ions. However, although lithium titanate has good stability, the material has low electrical conductivity and lithium ion diffusion. The purpose of this research is to synthesis the spinel LTO using combinated hydrothermal and mechanochemical processes from xerogel TiO2. Then, to increase the conductivity, in the half-cell battery assembly process it was added acetylene black conductive (AB) additive with various from 10%, to 15% in wt. The LTO obtained were characterized using scanning electron microscope (SEM), X-Ray Diffraction (XRD) and Brunauer-Emmett-Teller (BET). The XRD showed a rutile as minor phase, while SEM showed homogeneous distribution of particle with an average particle size of 0.35 μm. The BET showed that the surface area of LTO formed is 2.26 m2/g. The assembled coin half cells used this Li4Ti5O12 as a cathode and lithium metal foil as the anode were tested using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and charge discharge (CD). The conductivity value obtained from EIS corresponds to the contents of AB. Meanwhile, the CV and CD testing showed that higher percentage of AB causing the decrease of battery specific capacity. The highest specific capacity at the rate of 10C is obtained at the mixture of 10wt% AB with the value of 40.91 mAh/g.

Isolation of 1,4-Li(2)-C(6)H(4) and its reaction with [(Ph(3)P)AuCl].

PubMed

Flower, Kevin R; McGown, A T; Miles, Philip J; Pritchard, Robin G; Warren, John E

2010-04-14

The difficulty in generating 1,4-Li2-C6H4 utilising the lithium halogen exchange reaction on 1,4-Br2-C6H4, 1,4-I2-C6H4 and 1-Br-4-I-C6H4 is revisited and only on treatment of 1,4-I2-C6H4 with 2 molar equivalents of n-BuLi can 1,4-Li2-C6H4 1 be isolated in excellent yield. Treatment of 1 with two equivalents of [ClAu(PPh3)] gives [1,4-(Ph3PAu)2-C6H4] 2a in excellent yield. Subsequent treatment of 2a with 2.5 molar equivalents of PPh2Me, PPhMe2 or PMe3 affords the PPh3 substituted compounds [1,4-(LAu)2-C6H4] (L = PPh2Me 2b, PPhMe2 2c, PMe3 2d) in essentially quantitative yields. On treatment of 1,4-Br2-C6H4 or 1-Br-4-I-C6H4 with 2 molar equivalents of n-BuLi only mono-lithiation takes place to give 1-Br-4-Li-C6H4 3 as shown through the isolation of essentially 1:1 molar equivalents of Ph2PC6H4-4-Br and Ph2PBu on treatment with 2 molar equivalents of ClPPh2. Treatment of 3, prepared by lithium/iodine exchange on 1-Br-4-I-C6H4, with [ClAu(PPh3)] affords [(Ph3P)Au(C6H4-4-Br)] 4 as expected and in addition [(Ph3P)Au(n-Bu)(C6H4-4-Br)2] 5, indicating the straightforward chloride/aryl exchange at gold may proceed in competition with oxidative addition of the n-BuI, generated in the initial lithium/iodine exchange reaction, to some aurate complex Li[Au(C6H4-4-Br)2] 6 formed in situ followed by reductive elimination of Br-C6H4-4-n-Bu in a manner that mimics lithium diorganocuprate chemistry. All of the gold-containing compounds have been spectroscopically characterised by 1H and 31P-{1H} NMR and in addition compounds 2a-d and 5 by single crystal X-ray diffraction studies. The solid state structures observed for 2a-d are dictated by non-conventional hydrogen bonding and the packing requirements of the phosphine ligands. For 2a and 2b there is no close Au...Au approach, however for 2c and 2d the reduction in the number of phenyl rings allows the formation of Au...Au contacts. For 2c and 2d the extended structures appear to be helical chains with Au...Au contact parameters of 3

Calcium cation enhanced cathode/electrolyte interface property of Li2FeSiO4/C cathode for lithium-ion batteries with long-cycling life

NASA Astrophysics Data System (ADS)

Qu, Long; Li, Mingtao; Tian, Xiaolu; Liu, Pei; Yi, Yikun; Yang, Bolun

2018-03-01

Currently, the cycle performance at low rate is one of the most critical factor for realizing practical applications of Li2FeSiO4/C as a cathode of the lithium-ion batteries. To meet this challenge, calcium (Ca)-doped Li2FeSiO4/C is prepared by using the sol-gel method with soluble Li, Fe, Si and Ca sources. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy measurements are carried out to determine the crystal structures, morphologies, particle sizes and chemical valence states of the resulting products. Rietveld refinement confirms that Ca-doped Li2FeSiO4 has a monoclinic P21/n structure and that a Ca cation occupies the Fe site in the Li2FeSiO4 lattice. The grain size of Ca-doped Li2FeSiO4 is approximately 20 nm and the nanoparticles are interconnected tightly with amorphous carbon layer. As a cathode material for the lithium-ion batteries, Li2Fe0.97Ca0.03SiO4/C delivers a high discharge capacity of 186 mAh g-1 at a 0.5 C rate. Its capacity retention after the 100th cycle reaches 87%, which increases by 25 percentage points compared with Li2FeSiO4/C. The Li2Fe0.97Ca0.03SiO4/C cathode exhibits good rate performance, with corresponding discharge capacities of 170, 157, 144 and 117 mAh g-1 at 1 C, 2 C, 5 C and 10 C rates, respectively. In summary, the improvement of the electrochemical performance can be attributed to a coefficient of the strengthened crystal structure stability during Li+ deintercalation-intercalation and restrained side reactions between electrode and electrolyte.

Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}: Structural, spectroscopic and computational studies on a sorosilicate

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

Kahlenberg, Volker, E-mail: volker.kahlenberg@uibk.ac.at; Brunello, Emanuele; Hejny, Clivia

2015-05-15

Synthesis experiments in the system Li{sub 2}O–CaO–SiO{sub 2} resulted in the formation of single-crystals of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. Structural investigations were based on single-crystal diffraction. At ambient conditions the compound has the following basic crystallographic data: hexagonal symmetry, space group P6{sub 1}22, a=5.0961(2) Å, c=41.264(2) Å, V=928.07(6) Å{sup 3}, Z=6. Structure solution was performed using direct methods. The final least-squares refinement calculations converged at a residual of R(|F|)=0.0260. From a structural point the lithium calcium silicate belongs to the group of pyrosilicates containing [Si{sub 2}O{sub 7}]-groups. Additional lithium and calcium cations are incorporated between the silicate dimers andmore » are coordinated by four and six nearest oxygen neighbours, respectively. Each [LiO{sub 4}]-tetrahedron shares two common corners with directly neighboring tetrahedra forming zweier single-chains which are running parallel to 〈1 0 0〉 in z-levels defined by the presence of the 6{sub 1}{sup [0} {sup 0} {sup 1]}-screw axes. From the corner-sharing [LiO{sub 4}]- and [SiO{sub 4}]-moieties a three dimensional framework can be constructed. An interesting feature of this framework is the presence of an O{sup [3]}-type bridging oxygen linking three tetrahedra (one [LiO{sub 4}]- and two [SiO{sub 4}]-units). Structural similarities with other silicates are discussed in detail. The high-temperature behavior of the Si–O, Ca–O and Li–O bond distances in Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} was investigated by in{sub -}situ single-crystal X-ray diffraction in the range between 65 and 700 °C. From the evolution of the lattice parameters, the thermal expansion tensor α{sub ij} has been determined. The structural characterization has been supplemented by micro-Raman spectroscopy. Interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT

Synthesis and performances of 2LiFePO4·Li3V2(PO4)3/C cathode materials via spray drying method with double carbon sources

NASA Astrophysics Data System (ADS)

Zhang, Jia-feng; Shen, Chao; Zhang, Bao; Zheng, Jun-chao; Peng, Chun-li; Wang, Xiao-wei; Yuan, Xin-bo; Li, Hui; Chen, Guo-min

2014-12-01

The 2LiFePO4·Li3V2(PO4)3/C samples are synthesized through spray drying method. Glucose and oxalic acid are used as collaborative carbon sources to improve the electrochemical performance of 2LiFePO4·Li3V2(PO4)3/C composites. XRD results reveal the LiFePO4·Li3V2(PO4)3/C samples are composed of orthorhombic LiFePO4 and monoclinic Li3V2(PO4)3 phases. SEM results reveal that the nano-spherical Fe4(VO4)4·5H2O are about 80 nm and the 2LiFePO4·Li3V2(PO4)3/C composites possess a micro-nano spherical morphology with carbon coating layer. The samples show the best electrochemical performance when the mass ration of glucose and oxalic is 6:4, it can deliver a capacity of 147.6 mAh g-1, 145.0 mAh g-1, 134.1 mAh g-1 and 123.0 mAh g-1 at the rates of 0.1C, 1C, 5C and 10C, respectively.

Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

2018-04-01

Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

Fabrication of lead-free piezoelectric Li2CO3-added (Ba,Ca)(Ti,Sn)O3 ceramics under controlled low oxygen partial pressure and their properties

NASA Astrophysics Data System (ADS)

Noritake, Kouta; Sakamoto, Wataru; Yuitoo, Isamu; Takeuchi, Teruaki; Hayashi, Koichiro; Yogo, Toshinobu

2018-02-01

Reduction-resistant lead-free (Ba,Ca)(Ti,Sn)O3 piezoceramics with high piezoelectric constants were fabricated by optimizing the amount of Li2CO3 added. Oxygen partial pressure was controlled during the sintering of (Ba,Ca)(Ti,Sn)O3 ceramics in a reducing atmosphere using H2-CO2 gas. Enhanced grain growth and a high-polarization state after poling treatment were achieved by adding Li2CO3. Optimizing the amount of Li2CO3 added to (Ba0.95Ca0.05)(Ti0.95Sn0.05)O3 ceramics sintered under a low oxygen partial pressure resulted in improved piezoelectric properties while maintaining the high sintered density. The prepared Li2CO3-added ceramic samples had homogeneous microstructures with a uniform dispersion of each major constituent element. However, the residual Li content in the 3 mol % Li2CO3-added (Ba0.95Ca0.05)(Ti0.95Sn0.05)O3 ceramics after sintering was less than 0.3 mol %. Sintered bodies of this ceramic prepared in a CO2 (1.5%)-H2 (0.3%)/Ar reducing atmosphere (PO2 = 10-8 atm at 1350 °C), exhibited sufficient electrical resistivity and a piezoelectric constant (d 33) exceeding 500 pC/N. The piezoelectric properties of this nonreducible ceramic were comparable or superior to those of the same ceramic sintered in air.

Biopolymer-modified graphite oxide nanocomposite films based on benzalkonium chloride-heparin intercalated in graphite oxide

NASA Astrophysics Data System (ADS)

Meng, Na; Zhang, Shuang-Quan; Zhou, Ning-Lin; Shen, Jian

2010-05-01

Heparin is a potent anticoagulant agent that interacts strongly with antithrombin III to prevent the formation of fibrin clots. In the present work, poly(dimethylsiloxane)(PDMS)/graphite oxide-benzalkonium chloride-heparin (PDMS/modified graphite oxide) nanocomposite films were obtained by the solution intercalation technique as a possible drug delivery system. The heparin-benzalkonium chloride (BAC-HEP) was intercalated into graphite oxide (GO) layers to form GO-BAC-HEP (modified graphite oxide). Nanocomposite films were characterized by XRD, SEM, TEM, ATR-FTIR and TGA. The modified graphite oxide was observed to be homogeneously dispersed throughout the PDMS matrix. The effect of modified graphite oxide on the mechanical properties of the nanocomposite film was investigated. When the modified graphite oxide content was lower than 0.2 wt%, the nanocomposites showed excellent mechanical properties. Furthermore, nanocomposite films become delivery systems that release heparin slowly to make the nanocomposite films blood compatible. The in vitro studies included hemocompatibility testing for effects on platelet adhesion, platelet activation, plasma recalcification profiles, and hemolysis. Results from these studies showed that the anticoagulation properties of PDMS/GO-BCA-HEP nanocomposite films were greatly superior to those for no treated PDMS. Cell culture assay indicated that PDMS/GO-BCA-HEP nanocomposite films showed enhanced cell adhesion.

Atomic-scale recognition of surface structure and intercalation mechanism of Ti3C2X.

PubMed

Wang, Xuefeng; Shen, Xi; Gao, Yurui; Wang, Zhaoxiang; Yu, Richeng; Chen, Liquan

2015-02-25

MXenes represent a large family of functionalized two-dimensional (2D) transition-metal carbides and carbonitrides. However, most of the understanding on their unique structures and applications stops at the theoretical suggestion and lack of experimental support. Herein, the surface structure and intercalation chemistry of Ti3C2X are clarified at the atomic scale by aberration-corrected scanning transmission electron microscope (STEM) and density functional theory (DFT) calculations. The STEM studies show that the functional groups (e.g., OH(-), F(-), O(-)) and the intercalated sodium (Na) ions prefer to stay on the top sites of the centro-Ti atoms and the C atoms of the Ti3C2 monolayer, respectively. Double Na-atomic layers are found within the Ti3C2X interlayer upon extensive Na intercalation via two-phase transition and solid-solution reactions. In addition, aluminum (Al)-ion intercalation leads to horizontal sliding of the Ti3C2X monolayer. On the basis of these observations, the previous monolayer surface model of Ti3C2X is modified. DFT calculations using the new modeling help to understand more about their physical and chemical properties. These findings enrich the understanding of the MXenes and shed light on future material design and applications. Moreover, the Ti3C2X exhibits prominent rate performance and long-term cycling stability as an anode material for Na-ion batteries.

Structure of salts of lithium chloride and lithium hexafluorophosphate as solvates with pyridine and vinylpyridine and structural comparisons: (C5H5N)LiPF6, [p-(CH2=CH)C5H4N]LiPF6, [(C5H5N)LiCl]n, and [p-(CH2=CH)C5H4N]2Li(μ-Cl)2Li[p-(CH2=CH)C5H4N]2.

PubMed

Jalil, AbdelAziz; Clymer, Rebecca N; Hamilton, Clifton R; Vaddypally, Shivaiah; Gau, Michael R; Zdilla, Michael J

2017-03-01

Due to the flammability of liquid electrolytes used in lithium ion batteries, solid lithium ion conductors are of interest to reduce danger and increase safety. The two dominating general classes of electrolytes under exploration as alternatives are ceramic and polymer electrolytes. Our group has been exploring the preparation of molecular solvates of lithium salts as alternatives. Dissolution of LiCl or LiPF 6 in pyridine (py) or vinylpyridine (VnPy) and slow vapor diffusion with diethyl ether gives solvates of the lithium salts coordinated by pyridine ligands. For LiPF 6 , the solvates formed in pyridine and vinylpyridine, namely tetrakis(pyridine-κN)lithium(I) hexafluorophosphate, [Li(C 5 H 5 N) 4 ]PF 6 , and tetrakis(4-ethenylpyridine-κN)lithium(I) hexafluorophosphate, [Li(C 7 H 7 N) 4 ]PF 6 , exhibit analogous structures involving tetracoordinated lithium ions with neighboring PF 6 - anions in the I-4 and Aea2 space groups, respectively. For LiCl solvates, two very different structures form. catena-Poly[[(pyridine-κN)lithium]-μ 3 -chlorido], [LiCl(C 5 H 5 N)] n , crystalizes in the P2 1 2 1 2 1 space group and contains channels of edge-fused LiCl rhombs templated by rows of π-stacked pyridine ligands, while the structure of the LiCl-VnPy solvate, namely di-μ-chlorido-bis[bis(4-ethenylpyridine-κN)lithium], [Li 2 Cl 2 (C 7 H 7 N) 4 ], is described in the P2 1 /n space group as dinuclear (VnPy) 2 Li(μ-Cl) 2 Li(VnPy) 2 units packed with neighbors via a dense array of π-π interactions.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

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.

Effect of lightning strike on bromine intercalated graphite fiber/epoxy composites

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Brink, Norman O.

1991-01-01

Laminar composites were fabricated from pristine and bromine intercalated pitch based graphite fibers. It was found that laminar composites could be fabricated using either pristine or intercalated graphite fibers using standard fabrication techniques. The intercalated graphite fiber composites had electrical properties which were markedly improved over both the corresponding pitch based and polyacrylonitrile (PAN) based composites. Despite composites resistivities more than an order of magnitude lower for pitch based fiber composites, the lightning strike resistance was poorer than that of the Pan based fiber composites. This leads to the conclusion that the mechanical properties of the pitch fibers are more important than electrical or thermal properties in determining the lightning strike resistance. Based on indicated lightning strike tolerance for high elongation to failure materials, the use of vapor grown, rather than pitch based graphite fibers appears promising.

Synthesis and characterization of intercalated few-layer graphenes

NASA Astrophysics Data System (ADS)

Sato, Shogo; Ichikawa, Hiroaki; Iwata, Nobuyuki; Yamamoto, Hiroshi

2014-02-01

Toward achieving room-temperature superconductivity, FeCl3-intercalated few-layer graphenes (FeCl3-FLGs) and Ca-intercalated few-layer graphenes (Ca-FLGs) were synthesized. FeCl3-FLGs were synthesized by the two-zone method and Ca-FLGs were synthesized using Ca-Li alloy. The Raman spectra of the FeCl3-FLGs showed a lower-intensity peak at 1607 cm-1 than that of the corresponding bare G. The peak at 1607 cm-1 suggested that the sample was stage 4-5 FeCl3-FLGs. The room-temperature electrical resistivity of FeCl3-FLGs was 2.65 × 10-5 Ω·m, which linearly decreased with decreasing temperature with a marked change occurring at approximately 200 K. From a XRD pattern of Ca-FLGs, we concluded that Ca is intercalated in FLGs. The room-temperature resistivity of Ca-FLGs was 3.45 × 10-5 Ω·m, which increased with decreasing temperature.

Size dependence effect of carbon-based anode material on intercalation characteristics of Li-ion battery

NASA Astrophysics Data System (ADS)

Anwar, Miftahul; Jupri, Dwi Rahmat; Saraswati, Teguh Endah

2017-01-01

This work aims to study the effect of the different size of Li-ion battery anode during charging state. Carbon-Based nanomaterial using arc-discharge in a liquid which is much simpler and cheaper compared to other techniques, i.e., CVD, laser vaporization, etc. The experiment was performed using intermediate DC power supply (1300 W) to produce an arc, and commercial graphite pencils (with 5 mm diameter) as negative and positive electrodes. Deionized water mixed with ethanol was used as a heat absorber. The result shows that arc discharge in deionized water could effectively produce carbon nanomaterial (i.e., nano-onions). In addition, finite element method-based simulation of the different intercalating process of Li-ion to the different shape of the anode, i.e., bulk semi-porous and porous anode materials for battery application is also presented. The results show that intercalation of Li ions depends on the anode structure due to the different potential density at anode region. This finding will provide support for design of Li-ion battery based on carbon nanomaterial

Synthesis of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y Ceramic and its Application in Efficient Plasma Decomposition of CO2

NASA Astrophysics Data System (ADS)

Li, Ruixing; Tang, Qing; Yin, Shu; Sato, Tsugio

According to both the first principle and materials chemistry, a method for fabricating [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y ceramic was investigated. It was considered that the sintering was promoted by self-accelerated diffusion due to the formation of point defects caused by doping with Li2Si2O5. Consequently, a concept of non-stoichiometrically activated sintering, which was enhanced by point defects without the help of a grain boundary phase, was systematically studied in the Ca1-xSrxTiO3-Li2Si2O5 system. The mechanical and dielectric properties of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y were greatly enhanced by adding Li2Si2O5. To improve CO2 decomposition activity, [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y, which possesses both high permittivity and high dielectric strength was used as a dielectric barrier to decompose CO2 by dielectric barrier discharges (DBDs) plasma without using any catalyst and auxiliary substance. It successfully generated DBDs plasma and the CO2 conversion was much higher than that using an alumina or a silica glass barrier which was widely used as the dielectric barrier in previous studies.

Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-10

Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content ofmore » 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.« less

Bonding between graphene and MoS 2 monolayers without and with Li intercalation

DOE PAGES

Ahmed, Towfiq; Modine, N. A.; Zhu, Jian-Xin

2015-07-27

We performed density functional theory (DFT) calculations for a bi-layered heterostructure combining a graphene layer with a MoS 2 layer with and without intercalated Li atoms. Our calculations demonstrate the importance of the van der Waals (vdW) interaction, which is crucial for forming stable bonding between the layers. Our DFT calculation correctly reproduces the linear dispersion, or Dirac cone, feature at the Fermi energy for the isolated graphene monolayer and the band gap for the MoS 2 monolayer. For the combined graphene/MoS 2 bi-layer, we observe interesting electronic structure and density of states (DOS) characteristics near the Fermi energy, showingmore » both the gap like features of the MoS 2 layer and in-gap states with linear dispersion contributed mostly by the graphene layer. Our calculated total DOS in this vdW heterostructure reveals that the graphene layer significantly contributes to pinning the Fermi energy at the center of the band gap of MoS 2. We also find that intercalating Li ions in between the layers of the graphene/MoS2 heterostructure enhances the binding energy through orbital hybridizations between cations (Li adatoms) and anions (graphene and MoS 2 monolayers). Moreover, we calculate the dielectric function of the Li intercalated graphene/MoS 2 heterostructure, the imaginary component of which can be directly compared with experimental measurements of optical conductivity in order to validate our theoretical prediction. We observe sharp features in the imaginary component of the dielectric function, which shows the presence of a Drude peak in the optical conductivity, and therefore metallicity in the lithiated graphene/MoS 2 heterostructure.« less

Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode.

PubMed

Cho, Sanghun; Ahn, Yong-Keon; Yin, Zhenxing; You, Duck-Jae; Kim, Hyunjin; Piao, Yuanzhe; Yoo, Jeeyoung; Kim, Youn Sang

2017-08-25

A novel copper oxide/graphite composite (GCuO) anode with high capacity and long cycle stability is proposed. A simple, one-step synthesis method is used to prepare the GCuO, through heat treatment of the Cu ion complex and pristine graphite. The gases generated during thermal decomposition of the Cu ion complex (H 2 and CO 2 ) induce interlayer expansion of the graphite planes, which assists effective ion intercalation. Copper oxide is formed simultaneously as a high-capacity anode material through thermal reduction of the Cu ion complex. Material analyses reveal the formation of Cu oxide nanoparticles and the expansion of the gaps between the graphite layers from 0.34 to 0.40 nm, which is enough to alleviate layer stress for reversible ion intercalation for Li or Na batteries. The GCuO cell exhibits excellent Li-ion battery half-cell performance, with a capacity of 532 mAh g -1 at 0.2 C (C-rate) and capacity retention of 83 % after 250 cycles. Moreover, the LiFePO 4 /GCuO full cell is fabricated to verify the high performance of GCuO in practical applications. This cell has a capacity of 70 mAh g -1 and a coulombic efficiency of 99 %. The GCuO composite is therefore a promising candidate for use as an anode material in advanced Li- or Na-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing the High-Voltage Cycling Performance of LiNi1/3Co1/3Mn1/3O2/Graphite Batteries Using Alkyl 3,3,3-Trifluoropropanoate as an Electrolyte Additive.

PubMed

Zheng, Xiangzhen; Huang, Tao; Pan, Ying; Wang, Wenguo; Fang, Guihuang; Ding, Kaining; Wu, Maoxiang

2017-06-07

The present study demonstrates that the use of alkyl 3,3,3-trifluoropropanoate, including methyl 3,3,3-trifluoropropanoate (TFPM) and ethyl 3,3,3-trifluoropropanoate (TFPE), as new electrolyte additive can dramatically enhance the high-voltage performance of LiNi 1/3 Co 1/3 Mn 1/3 O 2 /graphite lithium-ion batteries (3.0-4.6 V, vs Li/Li + ). The capacity retention was significantly increased from 45.6% to 75.4% after 100 charge-discharge cycles due to the addition of 0.2 wt % TFPM in the electrolyte, and significantly increased from 45.6% to 76.1% after 100 charge-discharge cycles due to the addition of 0.5 wt % TFPE in the electrolyte, verifying their suitability in this application. Electrochemical impedance spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to study the effect of TFPM and TFPE on cell performance. The data indicates that the improved cycling activity can be ascribed to the participation of TFPM or TFPE in the formation of a thinner cathode/electrolyte interfacial film, thereby enhancing the cell cycling performance owing to a reduced interfacial resistance at high voltage.

Insights into the Li Intercalation and SEI Formation on LiSi Nanoclusters

DOE PAGES

Hankins, Kie; Soto, Fernando A.; Balbuena, Perla B.

2017-01-01

We report a first-principles atomic level assessment of the lithiation and reactivity of pre-lithiated Si clusters. Density functional theory formation energy calculations reveal that the pre-lithiated Li 16Si 16 cluster exposed to two different Li fluxes can store Li between the concentrations of Li 2.5Si and Li 3.5Si. This increase in storage capacity is attributed to the start of an amorphization process in the cluster, and more importantly these results show that the intercalation reaction can be controlled by the flux of the Li-ions. However, in a real battery, the lithiation of the anode occurs simultaneously to the electrode-electrolyte reactions.more » Here we simulate the solid-electrolyte interphase (SEI) formation and simultaneous lithiation of a Li 16Si 16 cluster in contact with two different electrolyte solutions: one with pure ethylene carbonate (EC), and another with a 1 M solution of LiPF 6 in EC. Our ab initio molecular dynamics simulations show that the solvent and salt are decomposed leading to the initial stages of the SEI layer formation and large part of the added Li becomes part of the SEI. Interestingly, the pure EC solution results in lower storage capacity and higher reactivity, whereas the presence of the salt causes the opposite effect: higher lithiation and reduced reactivity.« less

Superconductivity in Li-intercalated bilayer arsenene and hole-doped monolayer arsenene: a first-principles prediction

NASA Astrophysics Data System (ADS)

Chen, Jianyong; Ge, Yanfeng; Zhou, Wenzhe; Peng, Mengqi; Pan, Jiangling; Ouyang, Fangping

2018-06-01

Using first-principles calculations, we find Li-intercalated bilayer arsenene with AB stacking is dynamically stable, which is different from pristine bilayer with AA stacking. Electron–phonon coupling of the stable Li-intercalated bilayer arsenene are dominated by the low frequency vibrational modes (E″(1), (1), E‧(1) and acoustic modes) and lead to an superconductivity with T c  =  8.68 K with isotropical Eliashberg function. Small biaxial tensile strain (2%) can improve T c to 11.22 K due to the increase of DOS and phonon softening. By considering the fully anisotropic Migdal–Eliashberg theory, T c are found to be enhanced by 50% and exhibits a single anisotropic gap nature. In addition, considering its nearly flat top valence band which is favorable for high temperature superconductivity, we also explore the superconducting properties of hole-doped monolayer arsenene under different strains. the unstrained monolayer arsenene superconducts at T c  =  0.22 K with 0.1 hole/cell doping. By applying 3% biaxial strain, T c can be lifted up strikingly to 6.69 K due to a strong Fermi nesting of the nearly flat band. Then T c decreases slowly with strain. Our findings provide another insight to realize 2D superconductivity and suggest that the strain is crucial to further enhance the transition temperature.

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.

Infrared predissociation spectroscopy of M+ (C6H6)(1-4)(H2O)(1-2)Ar(0-1) cluster ions, M = Li, Na.

PubMed

Beck, Jordan P; Lisy, James M

2011-05-05

Infrared predissociation (IRPD) spectra of Li(+)(C(6)H(6))(1-4)(H(2)O)(1-2)Ar(0-1) and Na(+)(C(6)H(6))(2-4)(H(2)O)(1-2)Ar(1) are presented along with ab initio calculations. The results indicate that the global minimum energy structure for Li(+)(C(6)H(6))(2)(H(2)O)(2) has each water forming a π-hydrogen bond with the same benzene molecule. This bonding motif is preserved in Li(+)(C(6)H(6))(3-4)(H(2)O)(2)Ar(0-1) with the additional benzene ligands binding to the available free OH groups. Argon tagging allows high-energy Li(+)(C(6)H(6))(2-4)(H(2)O)(2)Ar isomers containing water-water hydrogen bonds to be trapped and detected. The monohydrated, Li(+) containing clusters contain benzene-water interactions with varying strength as indicated by shifts in OH stretching frequencies. The IRPD spectra of M(+)(C(6)H(6))(1-4)(H(2)O)(1-2)Ar are very different for lithium-bearing versus sodium-bearing cluster ions emphasizing the important role of ion size in determining the most favorable balance of competing noncovalent interactions.

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.

Effect of overcharge on Li(Ni0.5Mn0.3Co0.2)O2/graphite lithium ion cells with poly(vinylidene fluoride) binder. III - Chemical changes in the cathode

NASA Astrophysics Data System (ADS)

Bareño, Javier; Dietz Rago, Nancy; Dogan, Fulya; Graczyk, Donald G.; Tsai, Yifen; Naik, Seema R.; Han, Sang-Don; Lee, Eungje; Du, Zhijia; Sheng, Yangping; Li, Jianlin; Wood, David L.; Steele, Leigh Anna; Lamb, Joshua; Spangler, Scott; Grosso, Christopher; Fenton, Kyle; Bloom, Ira

2018-05-01

1.5 Ah pouch cells based on Li(Ni0.5Mn0.3Co0.2)O2 cathodes and graphite anodes, both containing poly (vinylidene fluoride) (PVDF) binders, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state of charge (SOC), at which point they vented. The cells were subsequently discharged to 0% SOC and disassembled under an inert atmosphere for characterization. A combination of X-ray photoelectron spectroscopy (XPS), scanning-electron microscopy (SEM), energy-dispersive spectroscopy (EDS), 6Li SSNMR, and X-ray diffraction (XRD) analysis of the NMC532 cathodes indicates the formation of a thin C- and O-rich cathode electrolyte interphase layer, progressive Li loss above 140% SOC, and retention of the bulk crystal structure at all states of charge.

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

PubMed

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-05-09

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

Effects of Ca/Sr ratio control on optical and scintillation properties of Eu-doped Li(Ca,Sr)AlF6 single crystals

NASA Astrophysics Data System (ADS)

Yokota, Yuui; Tanaka, Chieko; Kurosawa, Shunsuke; Yamaji, Akihiro; Ohashi, Yuji; Kamada, Kei; Nikl, Martin; Yoshikawa, Akira

2018-05-01

Eu-doped Li(Ca,Sr)AlF6 [Eu:LiCSAF] single crystals with various Ca/Sr ratios were grown by the micro-pulling-down method, and their optical and scintillation properties were investigated to reveal the effects of Ca/Sr ratio on optical and scintillation properties of the Eu:LiCSAF single crystals. The Li(Ca1-x-ySrxEuy)AlF6 single crystals could be grown in 0 ≤ x ≤ 0.1, 0.5 ≤ x ≤ 1.0 and y = 0.02 while the Eu:LiCSAF crystals with x = 0.2, 0.25 and 0.4 included two colquiriite-type phases with different lattice parameters. The Li(Ca1-x-ySrxEuy)AlF6 single crystal with x = 0.25 and y = 0.02 showed the highest light yield under neutron irradiation.

Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

DOE PAGES

Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.; ...

2016-03-18

Graphitic materials are very essential in energy conversion and storage because of their excellent chemical and electrical properties. The strategy for obtaining functional graphitic materials involves graphite oxidation and subsequent dissolution in aqueous media, forming graphene-oxide nanosheets (GNs). Restacked GNs contain substantial intercalated water that can react with heteroatom dopants or the graphene lattice during reduction. We demonstrate that removal of intercalated water using simple solvent treatments causes significant structural reorganization, substantially affecting the oxygen reduction reaction (ORR) activity and stability of nitrogen-doped graphitic systems. Amid contrasting reports describing the ORR activity of GN-based catalysts in alkaline electrolytes, we demonstratemore » superior activity in an acidic electrolyte with an onset potential of ~0.9 V, a half-wave potential (E ½) of 0.71 V, and a selectivity for four-electron reduction of >95%. Finally and further, durability testing showed E ½ retention >95% in N 2- and O 2-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.« less

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2/graphite lithium ion cells with poly(vinylidene fluoride) binder. III — Chemical changes in the cathode

DOE PAGES

Bareno, Javier; Dietz Rago, Nancy; Dogan, Fulya; ...

2018-01-17

Here, 1.5 Ah pouch cells based on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes and graphite anodes, both containing poly (vinylidene fluoride) (PVDF) binders, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state of charge (SOC), at which point they vented. The cells were subsequently discharged to 0% SOC and disassembled under an inert atmosphere for characterization. A combination of X-ray photoelectron spectroscopy (XPS), scanning-electron microscopy (SEM), energy-dispersive spectroscopy (EDS), 6Li SSNMR, and X-ray diffraction (XRD) analysis of the NMC532 cathodes indicates the formation of a thin C- and O-rich cathode electrolyte interphase layer, progressive Li lossmore » above 140% SOC, and retention of the bulk crystal structure at all states of charge.« less

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2/graphite lithium ion cells with poly(vinylidene fluoride) binder. III — Chemical changes in the cathode

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

Bareno, Javier; Dietz Rago, Nancy; Dogan, Fulya

Here, 1.5 Ah pouch cells based on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes and graphite anodes, both containing poly (vinylidene fluoride) (PVDF) binders, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state of charge (SOC), at which point they vented. The cells were subsequently discharged to 0% SOC and disassembled under an inert atmosphere for characterization. A combination of X-ray photoelectron spectroscopy (XPS), scanning-electron microscopy (SEM), energy-dispersive spectroscopy (EDS), 6Li SSNMR, and X-ray diffraction (XRD) analysis of the NMC532 cathodes indicates the formation of a thin C- and O-rich cathode electrolyte interphase layer, progressive Li lossmore » above 140% SOC, and retention of the bulk crystal structure at all states of charge.« less

Intercalation of the layered solid acid HCa/sub 2/Nb/sub 3/O/sub 10/ by organic amines

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

Jacobson, A.J.; Johnson, J.W.; Lewandowski, J.T.

1987-01-01

Layered compounds of formula C/sub n/H/sub 2n+1/NH/sub 3/Ca/sub 2/Nb/sub 3/O/sub 10/ are formed by reaction of n-alkylamines with the solid acid HCa/sub 2/Nb/sub 3/O/sub 10/. Other organic bases such as pyridine can also be intercalated. The lattice constants of the new compounds have been determined by powder X-ray diffraction. The unit cells are tetragonal with a axes that are unchanged with variation of the intercalated amine. The c axes lengths (layer spacings) vary systematically with the hydrocarbon chain length of the alkylamine.

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives

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.

Structure and Dielectric Properties of (Sr0.2Ca0.488Nd0.208) TiO3-Li3NbO4 Ceramic Composites

NASA Astrophysics Data System (ADS)

Xia, C. C.; Chen, G. H.

2017-12-01

The new ceramic composites of (1-x) Li3NbO4-x (Sr0.2Ca0.488Nd0.208)TiO3 were prepared by the conventional solid state reaction method. The sintering behavior, phase composition, microstructure and microwave dielectric properties of the ceramics were investigated specially. The SEM and XRD results show that (1-x) Li3NbO4-x (Sr0.2Ca0.488Nd0.208) TiO3 (0.35≤x≤0.5) composites were composed of two phase, i.e. perovskite and Li3NbO4. With the increase of x, the ɛr increases from 27.1 to 38.7, Q×f decreases from 55000 GHz to 16770 GHz, and the τ f increases from -49 ppm/°C to 226.7 ppm/°C. The optimized dielectric properties with ɛr∼31.4, Q×f~16770GHz and τf~-8.1ppm/°C could be obtained as x=0.4 sintered at 1100°C for 4h. The as-prepared ceramic is expected to be used in resonators, filters, and other microwave devices.

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.

Atomic intercalation to measure adhesion of graphene on graphite

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

Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin

The interest in mechanical properties of layered and 2D materials has reemerged in light of device concepts that take advantage of flexing, adhesion and friction in such systems. Here we provide an effective measurement of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG) based on the analysis of atomic intercalates in graphite. Atomic intercalation is carried out using conventional ion sputtering, creating blisters in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory are used to reconstruct the atomic positions and the strain map withinmore » the deformed graphene sheet, as well as to demonstrate subsurface diffusion of the ions creating such blisters. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of 0.221 ± 0.011 J/m -2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that macroscopic mechanical properties of graphene scale down to at least a few nanometers length. The simplicity of our method, compared to the macroscale characterization, enables analysis of elastic mechanical properties in two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale.« less

Atomic intercalation to measure adhesion of graphene on graphite

DOE PAGES

Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; ...

2016-10-31

The interest in mechanical properties of layered and 2D materials has reemerged in light of device concepts that take advantage of flexing, adhesion and friction in such systems. Here we provide an effective measurement of the nanoscale elastic adhesion of a graphene sheet atop highly ordered pyrolytic graphite (HOPG) based on the analysis of atomic intercalates in graphite. Atomic intercalation is carried out using conventional ion sputtering, creating blisters in the top-most layer of the HOPG surface. Scanning tunneling microscopy coupled with image analysis and density functional theory are used to reconstruct the atomic positions and the strain map withinmore » the deformed graphene sheet, as well as to demonstrate subsurface diffusion of the ions creating such blisters. To estimate the adhesion energy we invoke an analytical model originally devised for macroscopic deformations of graphene. This model yields a value of 0.221 ± 0.011 J/m -2 for the adhesion energy of graphite, which is in surprisingly good agreement with reported experimental and theoretical values. This implies that macroscopic mechanical properties of graphene scale down to at least a few nanometers length. The simplicity of our method, compared to the macroscale characterization, enables analysis of elastic mechanical properties in two-dimensional layered materials and provides a unique opportunity to investigate the local variability of mechanical properties on the nanoscale.« less

Thermal conductivity of Ca3Co2O6 single crystals

NASA Astrophysics Data System (ADS)

Che, H. L.; Shi, J.; Wu, J. C.; Rao, X.; Liu, X. G.; Zhao, X.; Sun, X. F.

2018-05-01

Ca3Co2O6 is a rare example of one-dimensional Ising spin-chain material with the moments preferentially aligned along the c axis. In this work, we study the c-axis thermal conductivity (κc) of Ca3Co2O6 single crystal at low temperatures down to 0.3 K and in magnetic fields up to 14 T. The zero-field κc(T) shows a large phonon peak and can be well fitted by using the classical Debye model, which indicates that the heat transport is purely phononic. Moreover, the low-T κc(H) isotherms with H || c display a field-independent behavior. These results indicate that there is no contribution of magnetic excitations to the thermal conductivity in Ca3Co2O6, neither carrying heat nor scattering phonons, which can be attributed to the Ising-like spin anisotropy.

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

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

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

DOE PAGES

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham; ...

2018-06-16

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

From Metal-Organic Framework to Li2S@C-Co-N Nanoporous Architecture: A High-Capacity Cathode for Lithium-Sulfur Batteries.

PubMed

He, Jiarui; Chen, Yuanfu; Lv, Weiqiang; Wen, Kechun; Xu, Chen; Zhang, Wanli; Li, Yanrong; Qin, Wu; He, Weidong

2016-12-27

Owing to the high theoretical specific capacity (1166 mAh g -1 ), lithium sulfide (Li 2 S) has been considered as a promising cathode material for Li-S batteries. However, the polysulfide dissolution and low electronic conductivity of Li 2 S limit its further application in next-generation Li-S batteries. In this report, a nanoporous Li 2 S@C-Co-N cathode is synthesized by liquid infiltration-evaporation of ultrafine Li 2 S nanoparticles into graphitic carbon co-doped with cobalt and nitrogen (C-Co-N) derived from metal-organic frameworks. The obtained Li 2 S@C-Co-N architecture remarkably immobilizes Li 2 S within the cathode structure through physical and chemical molecular interactions. Owing to the synergistic interactions between C-Co-N and Li 2 S nanoparticles, the Li 2 S@C-Co-N composite delivers a reversible capacity of 1155.3 (99.1% of theoretical value) at the initial cycle and 929.6 mAh g -1 after 300 cycles, with nearly 100% Coulombic efficiency and a capacity fading of 0.06% per cycle. It exhibits excellent rate capacities of 950.6, 898.8, and 604.1 mAh g -1 at 1C, 2C, and 4C, respectively. Such a cathode structure is promising for practical applications in high-performance Li-S batteries.

Pressure-induced superconductivity in CaC2

PubMed Central

Li, Yan-Ling; Luo, Wei; Zeng, Zhi; Lin, Hai-Qing; Mao, Ho-kwang; Ahuja, Rajeev

2013-01-01

Carbon can exist as isolated dumbbell, 1D chain, 2D plane, and 3D network in carbon solids or carbon-based compounds, which attributes to its rich chemical binding way, including sp-, sp2-, and sp3-hybridized bonds. sp2-hybridizing carbon always captures special attention due to its unique physical and chemical property. Here, using an evolutionary algorithm in conjunction with ab initio method, we found that, under compression, dumbbell carbon in CaC2 can be polymerized first into 1D chain and then into ribbon and further into 2D graphite sheet at higher pressure. The C2/m structure transforms into an orthorhombic Cmcm phase at 0.5 GPa, followed by another orthorhombic Immm phase, which is stabilized in a wide pressure range of 15.2–105.8 GPa and then forced into MgB2-type phase with wide range stability up to at least 1 TPa. Strong electron–phonon coupling λ in compressed CaC2 is found, in particular for Immm phase, which has the highest λ value (0.562–0.564) among them, leading to its high superconducting critical temperature Tc (7.9∼9.8 K), which is comparable with the 11.5 K value of CaC6. Our results show that calcium not only can stabilize carbon sp2 hybridization at a larger range of pressure but also can contribute in superconducting behavior, which would further ignite experimental and theoretical interest in alkaline–earth metal carbides to uncover their peculiar physical properties under extreme conditions. PMID:23690580

Technological hurdles to the application of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.

1988-01-01

Before intercalated graphite fibers can be developed as an effective power material, there are several technological hurdles which must be overcome. These include the environmental stability, homogeneity and bulk properties, connection procedures, and costs. Strides were made within the last several years in stability and homogeneity of intercalated graphite fibers. Bulk properties and connection procedures are areas of active research now. Costs are still prohibitive for all but the most demanding applications. None of these problems, however, appear to be unsolvable, and their solution may result in wide spread GOC application. The development of a relatively simple technology application, such as EMI shielding, would stimulate the solution of scale-up problems. Once this technology is developed, then more demanding applications, such as power bus bars, may be possible.

Intercalated graphite fiber composites as EMI shields in aerospace structures

NASA Technical Reports Server (NTRS)

Gaier, James R.

1990-01-01

The requirements for electromagnetic interference (EMI) shielding in aerospace structures are complicated over that of ground structures by their weight limitations. As a result, the best EMI shielding materials must blend low density, high strength, and high elastic modulus with high shielding ability. In addition, fabrication considerations including penetrations and joints play a major role. The EMI shielding properties are calculated for shields formed from pristine and intercalated graphite fiber/epoxy composites and compared to preliminary experimental results and to shields made from aluminum. Calculations indicate that EMI shields could be fabricated from intercalated graphite composites which would have less than 12 percent of the mass of conventional aluminum shields, based on mechanical properties and shielding properties alone.

High voltage and high specific capacity dual intercalating electrode Li-ion batteries

NASA Technical Reports Server (NTRS)

Blanco, Mario (Inventor); West, William C. (Inventor)

2010-01-01

The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

A Lithium-ion Battery Using Partially Lithiated Graphite Anode and Amphi-redox LiMn2O4 Cathode.

PubMed

Jeon, Yuju; Noh, Hyun Kuk; Song, Hyun-Kon

2017-11-01

Delithiation followed by lithiation of Li + -occupied (n-type) tetrahedral sites of cubic LiMn 2 O 4 spinel (LMO) at ~4 [Formula: see text] (delivering ~100 mAh g LMO -1 ) has been used for energy storage by lithium ion batteries (LIBs). In this work, we utilized unoccupied (p-type) octahedral sites of LMO available for lithiation at ~3 [Formula: see text] (delivering additional ~100 mAh g LMO -1 ) that have never been used for LIBs in full-cell configuration. The whole capacity of amphi-redox LMO, including both oxidizable n-type and reducible p-type redox sites, at ~200 mAh g LMO -1 was realized by using the reactions both at 4 [Formula: see text] and 3 [Formula: see text]. Durable reversibility of the 3 V reaction was achieved by graphene-wrapping LMO nanoparticles (LMO@Gn). Prelithiated graphite (Li n C 6 , n < 1) was used as anodes to lithiate the unoccupied octahedral sites of LMO for the 3 V reaction.

Hydrothermal Synthesis, Crystal Structure, and Photoluminescent Properties of Li[UO2(CH3COO)3]3[Co(H2O)6

NASA Astrophysics Data System (ADS)

AlDamen, Murad A.; Juwhari, Hassan K.; Al-zuheiri, Aya M.; Alnazer, Louy A.

2017-12-01

Single crystal of Li[UO2(CH3COO)3]3[Co(H2O)6] was prepared and found to crystallize in the monoclinic crystal system in the sp. gr. C2/ c, with Z = 2, and unit cell parameters a = 22.1857(15) Å, b = 13.6477(8) Å, c = 15.6921(10) Å, β = 117.842(9)°, V = 4201.3(4) Å3. The crystal was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The single crystal X-ray diffraction analysis revealed that the crystal has a lamellar structure in which a cobalt hydrate is sandwiched within the Li[UO2(CH3COO)3]3 2- chains. Furthermore, the room temperature photoluminescence spectrum of the complex was investigated in the solid state.

Enhanced Hydrogen Storage Properties and Reversibility of LiBH4 Confined in Two-Dimensional Ti3C2.

PubMed

Zang, Lei; Sun, Weiyi; Liu, Song; Huang, Yike; Yuan, Huatang; Tao, Zhanliang; Wang, Yijing

2018-05-30

LiBH 4 is of particular interest as one of the most promising materials for solid-state hydrogen storage. Herein, LiBH 4 is confined into a novel two-dimensional layered Ti 3 C 2 MXene through a facile impregnation method for the first time to improve its hydrogen storage performance. The initial desorption temperature of LiBH 4 is significantly reduced, and the de-/rehydrogenation kinetics are remarkably enhanced. It is found that the initial desorption temperature of LiBH 4 @2Ti 3 C 2 hybrid decreases to 172.6 °C and releases 9.6 wt % hydrogen at 380 °C within 1 h, whereas pristine LiBH 4 only releases 3.2 wt % hydrogen under identical conditions. More importantly, the dehydrogenated products can partially rehydrogenate at 300 °C and under 95 bar H 2 . The nanoconfined effect caused by unique layered structure of Ti 3 C 2 can hinder the particles growth and agglomeration of LiBH 4 . Meanwhile, Ti 3 C 2 could possess superior effect to destabilize LiBH 4 . The synergetic effect of destabilization and nanoconfinement contributes to the remarkably lowered desorption temperature and improved de-/rehydrogenation kinetics.

Properties and Crystallization Phenomena in Li2Si2O5-Ca5(PO4)3F and Li2Si2O5-Sr5(PO4)3F Glass-Ceramics Via Twofold Internal Crystallization.

PubMed

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass-ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass-ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F(-) were prepared within the glasses of the SiO2-Li2O-K2O-CaO/SrO-Al2O3-P2O5-F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass-ceramics was established. The microstructures of the glass-ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass-ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass-ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass-ceramics. The authors conclude that the twofold crystallization of Li2Si2O5-Ca5(PO4)3F or Li2Si2O5-Sr5(PO4)3F glass-ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass-ceramics and, hence, displays new potential for dental applications.

First-principles theory of cation and intercalation ordering in Li xCoO 2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

Several types of cation- and vacancy-ordering are of interest in the Li xCoO 2 battery cathode material since they can have a profound effect on the battery voltage. We present a first-principles theoretical approach which can be used to calculate both cation- and vacancy-ordering patterns at both zero and finite temperatures. This theory also provides quantum-mechanical predictions (i.e., without the use of any experimental input) of battery voltages of both ordered and disordered Li xCoO 2/Li cells from the energetics of the Li intercalation reactions. Our calculations allow us to search the entire configurational space to predict the lowest-energy ground-state structures, search for large voltage cathodes, explore metastable low-energy states, and extend our calculations to finite temperatures, thereby searching for order-disorder transitions and states of partial disorder. We present the first prediction of the stable spinel structure LiCo 2O 4 for the 50% delithiated Li 0.5CoO 2.

Complete Decomposition of Li2CO3 in Li-O2 Batteries Using Ir/B4C as Noncarbon-Based Oxygen Electrode.

PubMed

Song, Shidong; Xu, Wu; Zheng, Jianming; Luo, Langli; Engelhard, Mark H; Bowden, Mark E; Liu, Bin; Wang, Chong-Min; Zhang, Ji-Guang

2017-03-08

Instability of carbon-based oxygen electrodes and incomplete decomposition of Li 2 CO 3 during charge process are critical barriers for rechargeable Li-O 2 batteries. Here we report the complete decomposition of Li 2 CO 3 in Li-O 2 batteries using the ultrafine iridium-decorated boron carbide (Ir/B 4 C) nanocomposite as a noncarbon based oxygen electrode. The systematic investigation on charging the Li 2 CO 3 preloaded Ir/B 4 C electrode in an ether-based electrolyte demonstrates that the Ir/B 4 C electrode can decompose Li 2 CO 3 with an efficiency close to 100% at a voltage below 4.37 V. In contrast, the bare B 4 C without Ir electrocatalyst can only decompose 4.7% of the preloaded Li 2 CO 3 . Theoretical analysis indicates that the high efficiency decomposition of Li 2 CO 3 can be attributed to the synergistic effects of Ir and B 4 C. Ir has a high affinity for oxygen species, which could lower the energy barrier for electrochemical oxidation of Li 2 CO 3 . B 4 C exhibits much higher chemical and electrochemical stability than carbon-based electrodes and high catalytic activity for Li-O 2 reactions. A Li-O 2 battery using Ir/B 4 C as the oxygen electrode material shows highly enhanced cycling stability than those using the bare B 4 C oxygen electrode. Further development of these stable oxygen-electrodes could accelerate practical applications of Li-O 2 batteries.

Synthèse et étude structrale de lyonsite-type (Na0,4,Li0,6)(Fe,Li2)(MoO4)3

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2015-01-01

The new compound (Na0.4,Li0.6)(Fe,Li2)(MoO4)3 was synthesized by cooling from the melt. Its anionic framework is built up from two distinct MO6 octa­hedra, each containing disordered Li+ and Fe3+ ions in 0.6:0.4 and 0.7:0.3 ratios, and two MoO4 tetra­hedra, which link by vertex-sharing of their O atoms. These tetra­meric units are further linked by sharing edges between octa­hedra and by formation of M—O—Mo (M = Fe/Li) bridges, forming ribbons propagating in the [100] direction. The ribbons are cross-linked in both the b- and c-axis directions, giving rise to a three-dimensional framework having [100] tunnels in which the monovalent Na+/Li+ cations (0.4:0.6 ratio) lie. Bond-valence calculations are consistent with the disorder model for the cations. The structure of the title compound, which is isotypic with Li3Fe(MoO4)3 and Li3Ga(MoO4)3, is compared briefly with those of LiFeMo2O8 and Li1.6Mn2.2(MoO4)3. PMID:26090130

Formation Dynamics of Potassium-Based Graphite Intercalation Compounds: An Ab Initio Study

NASA Astrophysics Data System (ADS)

Jiang, Xiankai; Song, Bo; Tománek, David

2018-04-01

This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. We use ab initio molecular dynamics simulations to study the microscopic dynamics of potassium intercalation in graphite. Upon adsorbing on graphite from the vapor phase, K atoms transfer their valence charge to the substrate. K atoms adsorbed on the surface diffuse rapidly along the graphene basal plane and eventually enter the interlayer region following a "U -turn" across the edge, gaining additional energy. This process is promoted at higher coverages associated with higher K pressure, leading to the formation of a stable intercalation compound. We find that the functionalization of graphene edges is an essential prerequisite for intercalation since bare edges reconstruct and reconnect, closing off the entry channels for the atoms.

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.

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

PubMed Central

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang; Pan, Chun-Jern; Chou, Hung-Lung; Chen, Hsin-An; Gong, Ming; Wu, Yingpeng; Yuan, Chunze; Angell, Michael; Hsieh, Yu-Ju; Chen, Yu-Hsun; Wen, Cheng-Yen; Chen, Chun-Wei; Hwang, Bing-Joe; Chen, Chia-Chun; Dai, Hongjie

2017-01-01

Recently, interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. Here, an aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of ∼110 mAh g−1 with Coulombic efficiency ∼98%, at a current density of 99 mA g−1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60 mAh g−1 at 6 C, over 6,000 cycles with Coulombic efficiency ∼ 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Finally, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode. PMID:28194027

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

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

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang

There has been some interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. An aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of B110 mAhg -1 with Coulombic efficiency B98%, at a current density of 99mAg -1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60mAhg -1 at 6 C, over 6,000 cycles with Coulombic efficiency Bmore » 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Lastly, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.« less

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

DOE PAGES

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang; ...

2017-02-13

There has been some interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. An aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of B110 mAhg -1 with Coulombic efficiency B98%, at a current density of 99mAg -1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60mAhg -1 at 6 C, over 6,000 cycles with Coulombic efficiency Bmore » 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Lastly, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.« less

Electrochemical behavior of LiV3O8 positive electrode in hybrid Li,Na-ion batteries

NASA Astrophysics Data System (ADS)

Maletti, S.; Sarapulova, A.; Tsirlin, A. A.; Oswald, S.; Fauth, F.; Giebeler, L.; Bramnik, N. N.; Ehrenberg, H.; Mikhailova, D.

2018-01-01

Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV3O8, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV3O8 can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg-1 after 10 cycles in the potential window of 0.8-3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li+ and Na+ cations into LiV3O8, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li0.7Na0.7V3O8 in Na-rich electrolytes, or to Li4V3O8 in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV3O8 are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li0.7Na0.7V3O8-type structure favors intercalation of Na+, whereas the LiV3O8-type prefers to accommodate Li+ cations.

Experimental high temperature carbon isotope fractionation involving graphite

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2016-12-01

Graphite/carbonate carbon isotope fractionation was mainly investigated at 400- 800°C and is based on empirical calibrations, theoretical calculations and few experiments [1,2]. Own work on COH-fluid/graphite isotope fractionation shows that in experiments up to 1000oC a fluid phase is always enriched in 13C compared to coexisting graphitic carbon. The eventual kinetic isotope effect in these experiments is best displayed by the graphitic carbon being at least 3 ‰ lighter than methane. Only few experiments done in the graphite/carbonate pair dealt with higher temperatures reaching 1400°C, indicating a fractionation of up to 2 ‰ at temperatures of the Earth's mantle [2-4]. To better understand carbon isotope fractionation in crustal systems and still overcome kinetic effects, we study the graphite/carbonatite pair with piston cylinder experiments in the Na2CO3-CaCO3-CaO-COH system. Tartaric acid (C4H6O6) supplies reduced carbon, time series are performed at 10 kbar, 1300-1800°C. Initial experiments at 1300°C produce well-ordered, micron-sized graphite flakes growing attached to the capsule walls while the Na-Ca-carbonatite-melt quenches to dendritic textures. No gaseous phase was observed. Conditions well above the liquidus of the Na2CO3-CaCO3-binary lead to dissolution of the H2O from tartaric acid decomposition in the melt, any CO2-component is bound by the excess CaO to CaCO3melt while in the relatively oxidizing capsule environment any CH4-component reacts with CO2 to carbon and H2O. The graphite and the carbonatite quench are measured for their δ13C composition using a GasBench II (carbonate-dissolution in phosphoric acid) and TC/EA (residual graphite combusted in oxygen atmosphere) system coupled to a Thermo Fischer IRMS. Our results expand from the graphite-carbonate system to graphite-fluid system when adding available fluid-carbonate fractionation factors, but are also directly applicable to diamond synthesis as graphite is often found as a

Effects of (LiCe) co-substitution on the structural and electrical properties of CaBi2Nb2O9 ceramics

NASA Astrophysics Data System (ADS)

Tian, Xiao-Xia; Qu, Shao-Bo; Du, Hong-Liang; Li, Ye; Xu, Zhuo

2012-03-01

The piezoelectric, dielectric, and ferroelectric properties of the (LiCe) co-substituted calcium bismuth niobate (CaBi2Nb2O9, CBNO) are investigated. The piezoelectric properties of CBNO ceramics are significantly enhanced and the dielectric loss tan δ decreased. This makes poling using (LiCe) co-substitution easier. The ceramics (where □ represents A-site Ca2+ vacancies, possess a pure layered structure phase and no other phases can be found. The Ca0.88(LiCe)0.04□0.04Bi2Nb2O9 ceramics possess optimal piezoelectric properties, with piezoelectric coefficient (d33) and Curie temperature (TC) found to be 13.3 pC/N and 960 °C, respectively. The dielectric and piezoelectric properties of the (LiCe) co-substituted CBNO ceramics exhibit very stable temperature behaviours. This demonstrates that the CBNO ceramics are a promising candidate for ultrahigh temperature applications.

Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

DOE PAGES

Byles, B. W.; West, P.; Cullen, D. A.; ...

2015-12-03

Extended hydrothermal treatment at an elevated temperature of 220 °C allowed high yield synthesis of manganese oxide nanowires with a todorokite crystal structure suitable for ions intercalation. The flexible, high aspect ratio nanowires are 50–100 nm in diameter and up to several microns long, with 3 × 3 structural tunnels running parallel to the nanowire longitudinal axis. Moreover, the tunnels are occupied by magnesium ions and water molecules, with the chemical composition found to be Mg 0.2MnO 2·0.5H 2O. The todorokite nanowires were, for the first time, electrochemically tested in both Li-ion and Na-ion cells. A first discharge capacity ofmore » 158 mA h g -1 was achieved in a Na-ion system, which was found to be greater than the first discharge capacity in a Li-ion system (133 mA h g -1). In spite of the large structural tunnel dimensions, todorokite showed a significant first cycle capacity loss in a Na-ion battery. After 20 cycles, the capacity was found to stabilize around 50 mA h g -1 and remained at this level for 100 cycles. In a Li-ion system, todorokite nanowires showed significantly better capacity retention with 78% of its initial capacity remaining after 100 cycles. Rate capability tests also showed superior performance of todorokite nanowires in Li-ion cells compared to Na-ion cells at higher current rates. Finally, these results highlight the difference in electrochemical cycling behavior of Li-ion and Na-ion batteries for a host material with spacious 3 × 3 tunnels tailored for large Na + ion intercalation.« less

The role of ionic liquid electrolyte in an aluminum–graphite electrochemical cell

DOE PAGES

Agiorgousis, Michael L.; Sun, Yi -Yang; Zhang, Shengbai

2017-02-17

Using first-principles calculations and molecular dynamics simulation, we study the working mechanism in an aluminum–graphite electrochemical cell, which was recently reported to exhibit attractive performance. We exclude the possibility of Al 3+ cation intercalation into graphite as in standard Li-ion batteries. Instead, we show that the AlCl 4 – anion intercalation mechanism is thermodynamically feasible. By including the ionic liquid electrolyte in the overall redox reaction, we are able to reproduce the high voltage observed in experiment. The active involvement of electrolyte in the reaction suggests that the evaluation of energy density needs to take the electrolyte into consideration. Here,more » our proposed structural model is consistent with the new peaks appearing in X-ray diffraction from the intercalation compound. The high rate capability is explained by the ultralow diffusion barriers of the AlCl 4 intercalant. With the clarified working mechanism, it becomes clear that the high voltage of the Al–graphite cell is a result of the thermodynamic instability of the AlCl 4-intercalated graphite.« less

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

Influence of solvent species on the charge-discharge characteristics of a natural graphite electrode

NASA Astrophysics Data System (ADS)

Fujimoto, Masahisa; Shoji, Yoshihiro; Kida, Yoshinori; Ohshita, Ryuji; Nohma, Toshiyuki; Nishio, Koji

The charge-discharge characteristics of a natural graphite electrode are examined in a mixed solvent composed of ethylene carbonate (EC) and propylene carbonate (PC). The characteristics are influenced largely by the solvent species. Natural graphite electrode displays good charge-discharge characteristics in an electrolyte containing EC with a high volume fraction. In an electrolyte containing PC, however, the electrode cannot be charged and the solvent is decomposed. X-ray photoelectron spectroscopy is used to obtain information about the surface of natural graphite. A thin LiF layer, the decomposition product of lithium hexafluorophosphate (LiPF 6), is formed on the surface of the natural graphite charged to 0.5 V (vs. Li/Li +) in an electrolyte containing a high volume fraction of EC. On the other hand, LiF and a carbonate compound are formed in the bulk and on the surface of natural graphite when the volume fraction of PC is high. These results suggest that the thin LiF layer, which is produced at a potential higher than 0.5 V (vs. Li/Li +) on the surface of natural graphite, enables the lithium ions to intercalate into the natural graphite without further decomposition of the electrolyte.

Improved electrochemical performances of LiSn2(PO4)3 anode material for lithium-ion battery prepared by solid-state method

NASA Astrophysics Data System (ADS)

Naren; Tian, Jianhua; Wang, Dongdong; Shan, Zhongqiang

2017-09-01

The rhombohedral LiSn2(PO4)3 was prepared by solid-state method for the anode material of lithium-ion battery. The effect of pH value of hydrothermal reaction system on the morphology of SnO2 as the precursor of LiSn2(PO4)3 and the influence of heat-treatment procedure and conditions, such as the sintering temperature and time, on the property of LiSn2(PO4)3 were investigated. The purity, morphology, structure and size distribution of prepared LiSn2(PO4)3 were characterized respectively by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) methods. The results demonstrate that the as-prepared LiSn2(PO4)3 particles exhibit rhombohedral single-crystal structure with an average particle size of 200 nm. The electrochemical measurement results reveal that the as-prepared LiSn2(PO4)3/C electrode exhibits the improved cycling stability and reversibility with a reversible discharge capacity of 448.6 mA h g-1 at 100 mA g-1 and better rate capability of 332.6 mA h g-1 at 500 mA g-1. The charge-discharge mechanism of LiSn2(PO4)3/C electrode was also investigated. According to the test results of cyclic voltammetry, the electrode process includes not only the intercalation and deintercalation of lithium ions in the LiSn2(PO4)3 particles, but also the surface pseudo-capacitive effect.

Properties and Crystallization Phenomena in Li2Si2O5–Ca5(PO4)3F and Li2Si2O5–Sr5(PO4)3F Glass–Ceramics Via Twofold Internal Crystallization

PubMed Central

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass–ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass–ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F− were prepared within the glasses of the SiO2–Li2O–K2O–CaO/SrO–Al2O3–P2O5–F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass–ceramics was established. The microstructures of the glass–ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass–ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass–ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass–ceramics. The authors conclude that the twofold crystallization of Li2Si2O5–Ca5(PO4)3F or Li2Si2O5–Sr5(PO4)3F glass–ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass–ceramics and, hence, displays new potential for dental applications. PMID:26389112

Ax(H3O)2-xMn5(HPO3)6 (A = Li, Na, K and NH4): open-framework manganese(ii) phosphites templated by mixed cationic species.

PubMed

Orive, Joseba; Fernández de Luis, Roberto; Fernández, Jesús Rodríguez; Lezama, Luis; Arriortua, María I

2016-07-26

Ax(H3O)2-xMn5(HPO3)6 (A = Li, x = 0.55 (1-Li); A = Na, x = 0.72 (2-Na); A = K, x = 0.30 (3-K); A = NH4, x = 0.59 (4-NH4)) phases were synthesized by employing mild hydrothermal conditions. 1-Li was studied by single crystal X-ray diffraction, while sodium, potassium and ammonium containing analogues were obtained as polycrystalline samples and characterized by powder X-ray diffraction. The four compounds were characterized by ICP-Q-MS, thermal analysis and XPS, IR, UV/Vis and EPR spectroscopy. Single crystal data indicate that 1-Li crystallizes in the P3[combining macron]c1 space group with lattice parameters a = 10.3764(1) Å and c = 9.4017(1) Å with Z = 2. The crystal structure of these phases is constituted by a three-dimensional [Mn(ii)5(HPO3)6](2-) anionic skeleton templated by alkali metal and ammonium cations together with protonated water molecules. Such an inorganic framework is formed by layers of edge-sharing MnO6 octahedra placed in the ab plane and joined along the c direction through phosphite pseudotetrahedra. The sheets display 12-membered ring channels parallel to the c-axis, ca. 5 Å in diameter, where the extraframework species display a strong disorder. EPR measurements point to the existence of short range ferromagnetic interactions around 12 K. Magnetic susceptibility and heat capacity measurements show that all the compounds exhibit long range antiferromagnetic order below circa 4 K, with a significant magnetocaloric effect around the Neel temperature.

Electrochemical Control of Copper Intercalation into Nanoscale Bi 2Se 3

DOE PAGES

Zhang, Jinsong; Sun, Jie; Li, Yanbin; ...

2017-02-20

Intercalation of exotic atoms or molecules into the layered materials remains an extensively investigated subject in current physics and chemistry. However, traditionally melt-growth and chemical interaction strategies are either limited by insufficiency of intercalant concentrations or destitute of accurate controllability. Here, we have developed a general electrochemical intercalation method to efficaciously regulate the concentration of zerovalent copper atoms into layered Bi 2Se 3, followed by comprehensive experimental characterization and analyses. Up to 57% copper atoms (Cu 6.7Bi 2Se 3) can be intercalated with no disruption to the host lattice. Meanwhile the unconventional resistance dip accompanied by a hysteresis loop belowmore » 40 K, as well as the emergence of new Raman peak in Cu xBi 2Se 3, is a distinct manifestation of the interplay between intercalated Cu atoms with Bi 2Se 3 host. Furthermore, our work demonstrates a new methodology to study fundamentally new and unexpected physical behaviors in intercalated metastable materials.« less

Sintering characteristic and microwave dielectric properties of 0.45Ca0.6Nd0.267TiO3-0.55Li0.5Nd0.5TiO3 ceramics with La2O3-B2O3-ZnO additive

NASA Astrophysics Data System (ADS)

Chen, Yawei; Zhang, Shuren; Li, Enzhu; Niu, Na; Yang, Hongcheng

2018-02-01

The La2O3-B2O3-ZnO (LBZ) glass was proved to be an effective sintering aid of the 0.45Ca0.6Nd0.26TiO3-0.55Li0.5Nd0.5TiO3 (CNT-LNT) ceramics. The influence of LBZ glass on the phase composition, low temperature sintering process, microstructure, activation energy, and dielectric properties of CNT-LNT ceramics was investigated in detail. The LBZ glass induced an obvious decrease of the CNT-LNT ceramics sintering temperature from 1350 to 1000 °C due to the liquid phase formation, which reduced the activation energy ( E a) of the CNT-LNT ceramics. In addition, the near zero temperature coefficient of resonant frequency (τƒ) value was obtained by adding moderate quantity of LBZ glass. CNT-LNT + 5 wt% LBZ (CNT-LNT + 5L) ceramics sintered at 1000°C/4 h displayed good microwave dielectric properties of: ɛ r = 101.7, Q × f = 1560 GHz ( f = 3.25 GHz) and τ ƒ = 2.3 ppm °C-1.

Lithium loss in the solid electrolyte interphase: Lithium quantification of aged lithium ion battery graphite electrodes by means of laser ablation inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Schwieters, Timo; Evertz, Marco; Mense, Maximilian; Winter, Martin; Nowak, Sascha

2017-07-01

In this work we present a new method using LA-ICP-MS to quantitatively determine the lithium content in aged graphite electrodes of a lithium ion battery (LIB) by performing total depth profiling. Matrix matched solid external standards are prepared using a solid doping approach to avoid elemental fractionation effects during the measurement. The results are compared and matched to the established ICP-OES technique for bulk quantification after performing a microwave assisted acid digestion. The method is applied to aged graphite electrodes in order to determine the lithium immobilization (= "Li loss") in the solid electrolyte interphase after the first cycle of formation. For this, different samples including a reference sample are created to obtain varying thicknesses of the SEI covering the electrode particles. By applying defined charging voltages, an initial lithiation process is performed to obtain specific graphite intercalation compounds (GICs, with target stoichiometries of LiC30, LiC18, LiC12 and LiC6). Afterwards, the graphite electrode is completely discharged to obtain samples without mobile, thus active lithium in its lattice. Taking the amount of lithium into account which originates from the residues of the LiPF6 (dissolved in the carbon components containing electrolyte), it is possible to subtract the amount of lithium in the SEI.

Kinetic Monte Carlo Study of Li Intercalation in LiFePO4.

PubMed

Xiao, Penghao; Henkelman, Graeme

2018-01-23

Even as a commercial cathode material, LiFePO 4 remains of tremendous research interest for understanding Li intercalation dynamics. The partially lithiated material spontaneously separates into Li-poor and Li-rich phases at equilibrium. Phase segregation is a surprising property of LiFePO 4 given its high measured rate capability. Previous theoretical studies, aiming to describe Li intercalation in LiFePO 4 , include both atomic-scale density functional theory (DFT) calculations of static Li distributions and entire-particle-scale phase field models, based upon empirical parameters, studying the dynamics of the phase separation. Little effort has been made to bridge the gap between these two scales. In this work, DFT calculations are used to fit a cluster expansion for the basis of kinetic Monte Carlo calculations, which enables long time scale simulations with accurate atomic interactions. This atomistic model shows how the phases evolve in Li x FePO 4 without parameters from experiments. Our simulations reveal that an ordered Li 0.5 FePO4 phase with alternating Li-rich and Li-poor planes along the ac direction forms between the LiFePO 4 and FePO 4 phases, which is consistent with recent X-ray diffraction experiments showing peaks associated with an intermediate-Li phase. The calculations also help to explain a recent puzzling experiment showing that LiFePO 4 particles with high aspect ratios that are narrower along the [100] direction, perpendicular to the [010] Li diffusion channels, actually have better rate capabilities. Our calculations show that lateral surfaces parallel to the Li diffusion channels, as well as other preexisting sites that bind Li weakly, are important for phase nucleation and rapid cycling performance.

Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation

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

Wang, Zhiguo; He, Yang; Gu, Meng

2016-09-21

Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystalmore » symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries and the approach for tailoring the functionalities of material based on insertion of ions in the lattice.« less

Recent Studies on Metal Oxides as Anodes for Li-ION Batteries

NASA Astrophysics Data System (ADS)

Sharma, N.; Subba Rao, G. V.; Chowdari, B. V. R.

Commercial lithium ion batteries (LIB) use layer-type compounds as the electrode materials and Li-ion conducting liquid or polymeric gel as the electrolyte. The preferred cathode and anode are LiCoO2 and graphite respectively. Efforts to improve the performance as well as safety-in-operation of LIB led to the search for alternate electrode materials. As regards the anodes, metal-oxide systems received special attention: Tin (Sn) containing mixed oxides and various 3d- and 4d- transition metal (M) mixed oxides. The reversible capacities in these systems arise either from alloying/de-alloying, formation/decomposition of Li2O aided by the nanosize metal (M) particles/Li-M-O bronze or Li-intercalation/de-intercalation. A brief account of the recent studies is presented.

On the difference between the pyroxenes LiFeSi2O6 and LiFeGe2O6 in their magnetic structures and spin orientations

NASA Astrophysics Data System (ADS)

Lee, Changhoon; Hong, Jisook; Shim, Ji Hoon; Whangbo, Myung-Hwan

2014-03-01

The clinopyroxenes LiFeSi2O6 and LiFeGe2O6, crystallizing in a monoclinic space group P21/c, are isostructural and isoelectronic Their crystal structures are made up of zigzag chains of edge-sharing FeO6 octahedra containing high-spin Fe3 + ions, which run along the c direction. Despite this structural similarity, the two have quite different magnetic structures and spin orientations. In LiFeSi2O6 the Fe spins have a ferromagnetic coupling within the zigzag chains along c and such FM chains have an antiferromagnetic coupling along a. In contrast, in LiFeGe2O6, the spins have an AFM coupling within the zigzag chains along c and such FM chains have an ↑ ↑ ↓ ↓ coupling along a. In addition, the spin orientation is parallel to c in LiFeSi2O6, but is perpendicular to c in LiFeGe2O6. To explain these differences in the magnetic structure and spin orientation, we evaluated the spin exchange parameters by performing energy mapping analysis based on LDA +U and GGA +U calculations and also by evaluating the magnetocrystalline anisotropy energies in terms of GGA +U +SOC and LDA +U +SOC calculations. Our study show that the magnetic structures and spin orientations of LiFeSi2O6 and LiFeGe2O6 are better described by LDA +U and LDA +U +SOC calculations. This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(2013R1A1A2060341).

Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

PubMed

Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

2016-06-22

Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C).

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

PubMed

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

Intercalation and controlled release properties of vitamin C intercalated layered double hydroxide

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

Gao, Xiaorui, E-mail: gxr_1320@sina.com; School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189; Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA

Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg–Al and Mg–Fe layered double hydroxides (LDHs) have been synthesized by the calcination–rehydration (reconstruction) method. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV–vis absorption spectroscopy indicate a successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the LDHs in deionised water and in aqueous CO{sub 3}{sup 2−} solutions imply that Mg{sub 3}Al–VC LDH is a better controlled release system than Mg{sub 3}Fe–VC LDH. Analysis of the release profiles using a number of kinetic models suggests a solution-dependent release mechanism, and amore » diffusion-controlled deintercalation mechanism in deionised water, but an ion exchange process in CO{sub 3}{sup 2−} solution. - Graphical abstract: Vitamin C anions have been intercalated in the interlayer space of layered double hydroxide and released in CO{sub 3}{sup 2−} solution and deionised water. - Highlights: • Vitamin C intercalated Mg–Al and Mg–Fe layered double hydroxides were prepared. • Release property of vitamin C in aqueous CO{sub 3}{sup 2−} solution is better. • Avrami-Erofe’ev and first-order models provide better fit for release results. • Diffusion-controlled and ion exchange processes occur in deionised water. • An ion exchange process occurs in CO{sub 3}{sup 2−} solution.« less

IR Li2Ga2GeS6 nanocrystallized GeS2-Ga2S3-Li2S electroconductive chalcogenide glass with good nonlinearity

PubMed Central

Liu, Qiming; Zhang, Peng

2014-01-01

GeS2-Ga2S3-Li2S electroconductive glasses were prepared by the conventional melt-quenching method through carefully controlling the heating rate. Comparing with the reference of glass-forming region, our investigated GeS2-Ga2S3-Li2S system was extended to the cation ratio of 0–20% Li with around 40% Ga. GeS2-Ga2S3-Li2S glass-ceramics containing IR Li2Ga2GeS6 nonlinear nanocrystals were obtained by the more carefully controlled heating rate. Its optical nonlinearity was investigated by the Maker fringe measurements, the maximum second harmonic intensity was observed to be 0.35 of the reference Z-cut quartz. IR Li2Ga2GeS6 nonlinear crystals were directly obtained at the composition of 40GeS2-30GaS1.5-30LiS0.5. PMID:25030713

Graphite intercalation compound with iodine as the major intercalant

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Kucera, Donald

1992-01-01

Halogenated CBr(sub x)I(sub y) (1 less than y/x less than 10) was made by exposing graphite materials with interplanar spacing in the 3.35 to 3.41 A range to either pure Br2 or an I2-Br2 mixture, and then to iodine vapor containing a small amount of Br2. The electrical resistivity of this product is from 3 to 6.5 times the pristine value. The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine to bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to fluorine attack during subsequent fluorination to fabricate graphite fluoride fibers.

High performance sulfur graphite full cell for next generation sulfur Li-ion battery

NASA Astrophysics Data System (ADS)

Wu, Yunwen; Momma, Toshiyuki; Yokoshima, Tokihiko; Nara, Hiroki; Osaka, Tetsuya

2018-06-01

Sulfur (S) Li-ion battery which use the metallic Li free anode is deemed as a promising solution to conquer the hazards originating from Li metal. However, stable cycling performance and low production price of the S Li-ion battery still remain challenging. Here, we propose a S-LixC full cell system by paring a S cathode and a pre-lithiated graphite anode which is cheap and commercially available. It shows stable cycling performance with a capacity around 1300 mAh (g-S)-1 at 0.2 C-rate and 1000 mAh (g-S)-1 at 0.5 C-rate. In addition, 0.1% per cycle capacity fading rate with a capacity retention of 880 mAh (g-S)-1 after 400 cycles at 0.2 C-rate has been achieved. The pre-formed solid electrolyte interphase (SEI) layer on the pre-lithaited graphite anode largely contributes to the high capacity performance. Notably, a 10-times-enlarged scale of S-LixC laminate type full cell has been assembled with high capacity performance (around 1000 mAh (g-S)-1) even after high rate cycling.

Unraveling the distinct luminescence thermal quenching behaviours of A/B-site Eu3+ ions in double perovskite Sr2CaMoO6:Eu3+

NASA Astrophysics Data System (ADS)

Wang, Chunhao; Ye, Shi; Zhang, Qinyuan

2018-01-01

Eu3+-doped Sr2CaMoO6 phosphors have a broad excitation band at around 350-425 nm, which meets the demand of Near-ultraviolet (NUV, 365-410 nm) absorption when applied in NUV-excitable phosphor-converted white light emitting diodes (WLEDs). The luminescence thermal quenching effects of Eu3+ ions at A/B sites (612 nm/593 nm) in Sr2CaMoO6 might be distinct with resultant emission colour variation, which is less studied but of significance for a scientific perspective. This research investigates on the temperature-dependent luminescence and decay curves of the nominal Sr1.9Li0.05Eu0.05CaMoO6 and Sr2Ca0.9Li0.05Eu0.05MoO6 phosphors. Results indicate that the luminescence of B-site Eu3+ ions is quenched more easily than that of A-site Eu3+ ions, directly evidenced by the fast and slow decay components in the decay curves. A distortion of B-site octahedron with elevating temperature and strong coupling with phonons may be partially responsible for the relatively poor thermal quenching behaviors of B-site Eu3+ ions. The research gives perspective on the thermal quenching of emissive lanthanide ions at different sites in phosphors.

Thermodynamic Investigation of the Eutectic Mixture of the LiNO3-NaNO3-KNO3-Ca(NO3)2 System

NASA Astrophysics Data System (ADS)

Peng, Qiang; Ding, Jing; Wei, Xiaolan; Jiang, Gan

2017-09-01

Molten nitrate salt is usually employed as heat transfer or energy storage medium in concentrating solar power systems to improve the overall efficiency of thermoelectric conversion. In the present work, the liquidus curves of the LiNO3-NaNO3-KNO3-Ca(NO3)2 system is determined by conformal ionic solution theory according to the solid-liquid equilibrium state of the binary mixture. The calculated eutectic temperature of the mixture is 93.17 {°}C, which is close to the experimental value of 93.22 {°}C obtained from differential scanning calorimetry (DSC). Visualization observation experiments reveal that the quaternary eutectic mixture begins to partially melt when the temperature reaches 50 {°}C, and the degree of melting increases with temperature. The mixture is completely melted at 130 {°}C. The observed changes in the dissolved state at different temperatures correlate well with the DSC heat flow curve fluctuations.

Two-Step Electrochemical Intercalation and Oxidation of Graphite for the Mass Production of Graphene Oxide.

PubMed

Cao, Jianyun; He, Pei; Mohammed, Mahdi A; Zhao, Xin; Young, Robert J; Derby, Brian; Kinloch, Ian A; Dryfe, Robert A W

2017-12-06

Conventional chemical oxidation routes for the production of graphene oxide (GO), such as the Hummers' method, suffer from environmental and safety issues due to their use of hazardous and explosive chemicals. These issues are addressed by electrochemical oxidation methods, but such approaches typically have a low yield due to inhomogeneous oxidation. Herein we report a two-step electrochemical intercalation and oxidation approach to produce GO on the large laboratory scale (tens of grams) comprising (1) forming a stage 1 graphite intercalation compound (GIC) in concentrated sulfuric acid and (2) oxidizing and exfoliating the stage 1 GIC in an aqueous solution of 0.1 M ammonium sulfate. This two-step approach leads to GO with a high yield (>70 wt %), good quality (>90%, monolayer), and reasonable oxygen content (17.7 at. %). Moreover, the as-produced GO can be subsequently deeply reduced (3.2 at. % oxygen; C/O ratio 30.2) to yield highly conductive (54 600 S m -1 ) reduced GO. Electrochemical capacitors based on the reduced GO showed an ultrahigh rate capability of up to 10 V s -1 due to this high conductivity.

Lithium salts for advanced lithium batteries: Li-metal, Li-O 2, and Li-S

DOE PAGES

Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik; ...

2015-06-01

Presently lithium hexafluorophosphate (LiPF 6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Li-metal), lithium-oxygen (Li-O 2), and lithium sulphur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical andmore » chemical reactions and conditions within such cells. Furthermore, this review explores the critical role Li-salts play in ensuring in these batteries viability.« less

Temperature-dependent OSL properties of nano-phosphors LiAlO2:C and α-Al2O3:C

NASA Astrophysics Data System (ADS)

Agarwal, Mini; Garg, Sandeep K.; Asokan, K.; Kumar, Pratik

2018-06-01

The present study focuses on the synthesis and characterization of carbon doped nano-phosphors, LiAlO2 and α-Al2O3 and their temperature-dependent optically stimulated luminescence (TA-OSL) characteristics in the temperature ranges of 25-350 °C. These nano-phosphors with the carbon concentration of 0.01 mol% exhibits high luminescent intensity for LiAlO2:C in the low dose range of 1 mGy-7 Gy and for α-Al2O3:C in the range of 100 mGy-1 kGy. Both these nano-phosphors are of polycrystalline in nature, having grain size 15-50 nm as confirmed by the X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM), respectively. The maximum TA-OSL intensities are observed at 125 °C for LiAlO2:C and 200 °C for Al2O3:C, and reveal the presence of deep defect centres. The Arrhenius analysis shows the activation energies Ea = 0.06 ± 0.02 eV for LiAlO2:C and Ea = 0.04 ± 0.01 eV, & Eb = 0.48 ± 0.07 eV for Al2O3:C. The TA-OSL and OSL characteristics are discussed with special reference to the medical and high radiation dosimetry. These compounds, LiAlO2:C and α-Al2O3:C, are non-toxic, robust and are potential candidates for reusable dosimetry.

Synthesis, crystal structure, and photocatalytic activity of a new two-layer Ruddlesden-Popper phase, Li{sub 2}CaTa{sub 2}O{sub 7}

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

Liang Zhenhua; Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026; Tang Kaibin

2008-04-15

A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. The detailed structure determination of Li{sub 2}CaTa{sub 2}O{sub 7} performed by powder X-ray diffraction (XRD) and electron microscopy (ED) shows that it crystallizes in the space group Fmmm [a{approx}5.5153(1), b{approx}5.4646(1), c{approx}18.2375(3)A]. UV-visible diffuse reflection spectrum of the prepared Li{sub 2}CaTa{sub 2}O{sub 7} indicates that it had absorption in the UV region. The photocatalytic activity of the Li{sub 2}CaTa{sub 2}O{sub 7} powders was evaluated by degradation of RhB molecules in water under ultra visible light irradiation. The results showed that Li{sub 2}CaTa{sub 2}O{sub 7} hasmore » high photocatalytic activity at room temperature. Therefore, the preparation and properties studies of Li{sub 2}CaTa{sub 2}O{sub 7} with a two-layer Ruddlesden-Popper structure suggest potential future applications in photocatalysis. - Graphical abstract: Crystal structure of a two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. Li{sub 2}CaTa{sub 2}O{sub 7} crystallizes in the space group Fmmm determined by powder X-ray and electron diffraction. UV-visible diffuse reflection spectra and the photocatalytic degradation of RhB molecules in water under ultra visible light irradiation show that Li{sub 2}CaTa{sub 2}O{sub 7} is a potential material in photocatalysis.« less

Controllable Self-Assembly of Micro-Nanostructured Si-Embedded Graphite/Graphene Composite Anode for High-Performance Li-Ion Batteries.

PubMed

Lin, Ning; Xu, Tianjun; Li, Tieqiang; Han, Ying; Qian, Yitai

2017-11-15

Si-containing graphite-based composites are considered as promising high-capacity anodes for lithium-ion batteries (LIBs). Here, a controllable and scalable self-assembly strategy is developed to produce micro-nanostructured graphite/Si/reduced graphene oxides composite (SGG). The self-assembly procedure is realized by the hydrogen bond interaction between acylamino-modified graphite and graphene oxides (GO); Si nanoparticles are in situ embedded between graphite and GO sheets uniformly. This architecture is able to overcome the incompatibility between Si nanoparticles and microsized graphite. Accordingly, the as-prepared SGG anode (Si 8 wt %) delivers a reversible Li-storage capacity of 572 mAh g -1 at 0.2 C, 502.2 mAh g -1 after 600 cycles at 0.8 C with a retention of 92%, and a capacity retention of 64% even at 10 C. The impressive electrochemical properties are ascribed to the stable architecture and three-dimensional conductive network constructed by graphite and graphene sheets, which can accommodate the huge volume change of Si, keep the conductive contact and structural integrity, and suppress side reactions with electrolyte. Additionally, the full-cell (LiFePO 4 cathode/SGG anode) delivers a specific capacity of 550 mAh g -1 with a working potential beyond 3.0 V.

The influence of temperature and salinity on the Li/Ca and d7Li of inorganic and biogenic carbonates

NASA Astrophysics Data System (ADS)

Marriott, C.; Staubwasser, M.; Crompton, R.; Henderson, G.

2003-04-01

Lithium is the sixth most abundant metal in the ocean. It is conservative with a residence time of around 1Ma and has two stable isotopes ^7Li and ^6Li that are not actively involved in biological processes. Isotopic fractionation is observed during incorporation into calcium carbonate but no previous work has systematically examined the controls on this fractionation. We have investigated Li incorporation and isotopic fraction in both inorganically precipitated calcite and coralline aragonite (1). In both cases there is an inverse correlation of Li concentration with temperature and no significant variation in isotopic fractionation. A decrease in D Li/Ca from 0.0092 to 0.0030 is seen over a temperature range of 5--30^oC, whilst an offset of approximately -8.5 ppm is seen in the δ^7Li ratio relative to the growth solution. The temperature dependence of Li/Ca has an increased sensitivity at low temperatures and might therefore be useful in examining changes in bottom water temperature. We are now investigating Li/Ca and δ^7Li of foraminifera. Previous work (2) has suggested little variability in Li/Ca with temperature, although this was for samples from warmer water where Li/Ca is not sensitive. In this study, Uvigerina are examined in a series of core top samples from the Arabian Sea with a depth range of 95--1800m and corresponding temperature range of 5--20^oC. A series of inorganic calcite samples have also been precipitated in order to examine the effect of salinity on Li/Ca, δ^7Li and δ44Ca over a salinity range of 10--50 psu. The distribution coefficient of Li shows a positive correlation with salinity over this range. δ^7Li and δ44Ca measurements for these samples are presently being analysed. (1) Marriott et al., 2002, GCA, 66, A485 (2) Delaney et al., 1985, GCA, 49, 1327

Effect of Vinylene Carbonate and Fluoroethylene Carbonate on SEI Formation on Graphitic Anodes in Li-Ion Batteries

DOE PAGES

Nie, Mengyun; Demeaux, Julien; Young, Benjamin T.; ...

2015-07-23

Binder free (BF) graphite electrodes were utilized to investigate the effect of electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) on the structure of the solid electrolyte interface (SEI). The structure of the SEI has been investigated via ex-situ surface analysis including X-ray Photoelectron spectroscopy (XPS), Hard XPS (HAXPES), Infrared spectroscopy (IR) and transmission electron microscopy (TEM). The components of the SEI have been further investigated via nuclear magnetic resonance (NMR) spectroscopy of D2O extractions. The SEI generated on the BF-graphite anode with a standard electrolyte (1.2 M LiPF6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC), 3/7more » (v/v)) is composed primarily of lithium alkyl carbonates (LAC) and LiF. Incorporation of VC (3% wt) results in the generation of a thinner SEI composed of Li2CO3, poly(VC), LAC, and LiF. Incorporation of VC inhibits the generation of LAC and LiF. Incorporation of FEC (3% wt) also results in the generation of a thinner SEI composed of Li2CO3, poly(FEC), LAC, and LiF. The concentration of poly(FEC) is lower than the concentration of poly(VC) and the generation of LAC is inhibited in the presence of FEC. The SEI appears to be a homogeneous film for all electrolytes investigated.« less

The synthesis and crystal structure of α-Ca 3UO 6

NASA Astrophysics Data System (ADS)

Holc, J.; Golic̆, L.

1983-07-01

Single crystals of α-Ca 3UO 6 were grown from a UO 3CaCl 2CaO melt by the slow cooling method from 950°C. The crystal structure was determined by means of X-ray diffraction with R = 0.032 and Rw = 0.019. The structure of α-Ca 3UO 6 is of Mg 3TeO 6 type. α-Ca 3UO 6 is rhombohedral with a = 6.729 (1)Å, α = 90.30 (1)°, Z = 2, Dc = 4.955 g/cm 3, Dm = 4.79 g/cm 3, space group R overline3. Uranium and calcium atoms are six-coordinated. At 1200°C rhombohedral α-Ca 3UO 6 irreversibly transforms to monoclinic β-Ca 3UO 6.

Highly Conducting Graphite Epoxy Composite Demonstrated

NASA Technical Reports Server (NTRS)

Gaier, James R.

1999-01-01

Weight savings as high as 80 percent could be achieved if graphite polymer composites could replace aluminum in structures such as electromagnetic interference shielding covers and grounding planes. This could result in significant cost savings, especially for the mobile electronics found in spacecraft, aircraft, automobiles, and hand-held consumer electronics. However, such composites had not yet been fabricated with conductivity sufficient to enable these applications. To address this lack, a partnership of the NASA Lewis Research Center, Manchester College, and Applied Sciences, Inc., fabricated nonmetallic composites with unprecedented electrical conductivity. For these composites, heat-treated, vapor-grown graphite fibers were selected which have a resistivity of about 80 mW-cm, more than 20 times more conductive than typical carbon fibers. These fibers were then intercalated with iodine bromide (IBr). Intercalation is the insertion of guest atoms or molecules between the carbon planes of the graphite fibers. Since the carbon planes are not highly distorted in the process, intercalation has little effect on mechanical and thermal properties. Intercalation does, however, lower the carbon fiber resistivity to less than 10 mW-cm, which is comparable to that of metal fibers. Scaleup of the reaction was required since the initial intercalation experiments would be carried out on 20-mg quantities of fibers, and tens of grams of intercalated fibers would be needed to fabricate even small demonstration composites. The reaction was first optimized through a time and temperature study that yielded fibers with a resistivity of 8.7 2 mW-cm when exposed to IBr vapor at 114 C for 24 hours. Stability studies indicated that the intercalated fibers rapidly lost their conductivity when exposed to temperatures as low as 40 C in air. They were not, however, susceptible to degradation by water vapor in the manner of most graphite intercalation compounds. The 1000-fold scaleup

Electrochemical preparation of carbon films with a Mo2C interlayer in LiCl-NaCl-Na2CO3 melts

NASA Astrophysics Data System (ADS)

Ge, Jianbang; Wang, Shuai; Zhang, Feng; Zhang, Long; Jiao, Handong; Zhu, Hongmin; Jiao, Shuqiang

2015-08-01

The electrodeposition of carbon films with a Mo2C interlayer was investigated in LiCl-NaCl-Na2CO3 melts at 900 °C. Cyclic voltammetry was applied to study the electrochemical reaction mechanism on Mo and Pt electrodes, indicating that, two reduction reactions including carbon deposition and carbon monoxide evolution, may take place on the two electrodes simultaneously during the cathodic sweep. Carbon films with a continuous Mo2C interlayer were prepared by constant voltage electrolysis, showing a good adhesion between Mo substrate and carbon films. The carbon films with a Mo2C interlayer were characterized using X-ray diffraction measurement, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The results reveal that carbon materials deposited on the electrodes are mainly composed of graphite and carbon diffusion in Mo (or Mo2C) leads to the formation and growth of Mo2C interlayer.

In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

PubMed

Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

2015-02-04

The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates.

Graphite fiber intercalation: Basic properties of copper chloride intercalated fibers

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Miller, J. D.

1986-01-01

In situ resistance measurements were used to follow the intercalation of copper chloride in pitch-based fibers. Subsequent single fiber resistivity measurements reveal a large range of resistivities, from 13 to 160 micro-ohms cm. Additional density measurements reveal a bimodal distribution of mass densities. The dense fibers have lower resistivities and correspond to the stage III compound identified by X-ray diffraction. Neither resistivity nor density correlate with diameter. Both energy dispersive spectroscopy and mass density data suggest that excess chlorine resides in the intercalated fiber, resulting in a stoichiometry of C4.9n CuCl2.5 (where n is the stage number) for the denser fibers. Finally, thermogravimetric analysis shows a 33 percent loss in mass upon heating to 700C. This loss in mass is attributed to loss of both chlorine and carbon.

Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

PubMed Central

Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

2016-01-01

A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method. PMID:27181195

Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability.

PubMed

Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

2016-05-16

A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li(+) diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe(3+) to Fe(2+) and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li(+) intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method.

Intercalated organic-inorganic perovskites stabilized by fluoroaryl-aryl interactions.

PubMed

Mitzi, David B; Medeiros, David R; Malenfant, Patrick R L

2002-04-22

Crystals of several new hybrid tin(II) iodide-based perovskites, involving 2,3,4,5,6- pentafluorophenethylammonium or phenethylammonium cation bilayers and intercalated aryl or perfluoroaryl molecules, were grown by slow evaporation of a methanol solution containing the hybrid perovskite and the intercalating species. The (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) structure was solved at -75 degrees C in a monoclinic C2/c subcell [a = 41.089(12) A, b = 6.134(2) A, c = 12.245(3) A, beta = 94.021(5) degrees, Z = 4] and consists of sheets of corner-sharing distorted SnI(6) octahedra separated by bilayers of pentafluorophenethylammonium cations. The intercalated benzene molecules form a single well-ordered layer interposed between adjacent fluoroaryl cation layers. The corresponding hybrid with an unfluorinated organic cation and fluorinated intercalating molecule, (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)), is isostructural [a = 40.685(4) A, b = 6.0804(6) A, c = 12.163(1) A, beta = 93.136(2) degrees, Z = 4]. For each intercalated system, close C...C contacts (3.44-3.50 A) between the aromatic cation and the intercalated molecule are indicative of a significant face-to-face interaction, similar to that found in the complex C(6)H(6).C(6)F(6). Crystal growth runs with the organic cation and prospective intercalating molecule either both fluorinated or both unfluorinated did not yield stable intercalated compounds, demonstrating the significance of fluoroaryl-aryl interactions in the current intercalated structures. Thermal analysis of (C(6)F(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)H(6)) and (C(6)H(5)C(2)H(4)NH(3))(2)SnI(4).(C(6)F(6)) crystals yields, in addition to the characteristic transitions of the parent perovskite, endothermic transitions [12.6(5) and 32.1(8) kJ/mol, respectively] with an onset at 145 degrees C and a weight loss corresponding to the complete loss of the intercalated molecule. The relatively high deintercalation temperature (well above the boiling point of

Hindered Glymes for Graphite-Compatible Electrolytes.

PubMed

Shanmukaraj, Devaraj; Grugeon, Sylvie; Laruelle, Stephane; Armand, Michel

2015-08-24

Organic carbonate mixtures are used almost exclusively as lithium battery electrolyte solvents. The linear compounds (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate) act mainly as thinner for the more viscous and high-melting ethylene carbonate but are the least stable component and have low flash points; these are serious handicaps for lifetime and safety. Polyethers (glymes) are useful co-solvents, but all formerly known representatives solvate Li(+) strongly enough to co-intercalate in the graphite negative electrode and exfoliate it. We have put forward a new electrolyte composition comprising a polyether to which a bulky tert-butyl group is attached ("hindered glyme"), thus completely preventing co-intercalation while maintaining good conductivity. This alkyl-carbonate-free electrolyte shows remarkable cycle efficiency of the graphite electrode, not only at room temperature, but also at 50 and 70 °C in the presence of lithium bis(fluorosulfonimide). The two-ethylene-bridge hindered glyme has a high boiling point and a flash point of 80 °C, a considerable advantage for safety. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A method to remove intercalates from bromine and iodine intercalated carbon fibers

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1993-01-01

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

A Solid State Ultraviolet Lasers Based on Cerium-Doped LiCaAIF(sub 6) Crystal Resonator

NASA Technical Reports Server (NTRS)

Yu, Nan; Le, Thanh; Schowalter, Steven J.; Rellergert, Wade; Jeet, Justin; Lin, Guoping; Hudson, Eric

2012-01-01

We report the first demonstration of a UV laser using a high-Q whispering gallery mode (WGM) resonator of Ce+: LiCaAlF6. We show that WGM resonators from LiCaAlF6 can achieve a Q of 2.6 x 10(sup 7) at UV. We demonstrated a UV laser at 290 nm with a pulsed pump laser at 266 nm. The experiments showed the low pump threshold intensity of 7.5 x 10(sup 9) W/m(sup 2) and slope efficiency of 25%. We have also observed lasing delay dynamics. These results are consistent with our modeling and theoretical estimates, and pave the way for a low threshold cw UV laser using WGM resonator cavity.

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

DOE PAGES

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi; ...

2016-12-13

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

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

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage† †Electronic supplementary information (ESI) available: Experimental and computational details, free energy plots for the NH3 evolution and N2 reduction with Co3N/Co, Fe4N/Fe, Mn5N2/Mn4N, Mo2N/Mo, CrN/Cr2N, TaN/Ta2N, NbN/Nb2N, Li3N/LiH, Ba3N2/BaH2, Sr3N2/SrH2, and Ca3N2/CaH2, surface oxidation energetics, ΔGvac[NH*x, yH*] based on gas phase H2 as hydrogen source, NH3 evolution with Fe-doped Mn4N, NH3 evolution with Mn6N2.58, Ca3N2 and Sr2N after correcting for partial nitride hydrolysis, NH3 yield from Ca3N2vs. time and H2 gas flow rate. See DOI: 10.1039/c5sc00789e

PubMed Central

Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A.

2015-01-01

The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH3), a fertilizer and chemical fuel, from N2 and H2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn6N2.58 to Mn4N and hydrogenation of Ca3N2 and Sr2N to Ca2NH and SrH2, respectively. PMID:29218166

High-pressure transitions of diopside and wollastonite: phase equilibria and thermochemistry of CaMgSi 2O 6, CaSiO 3 and CaSi 2O 5-CaTiSiO 5 system

NASA Astrophysics Data System (ADS)

Akaogi, M.; Yano, M.; Tejima, Y.; Iijima, M.; Kojitani, H.

2004-06-01

Phase transitions of CaMgSi 2O 6 diopside and CaSiO 3 wollastonite were examined at pressures to 23 GPa and temperatures to 2000 °C, using a Kawai-type multiavil apparatus. Enthalpies of high-pressure phases in CaSiO 3 and in the CaSi 2O 5-CaTiSiO 5 system were also measured by high-temperature calorimetry. At 17-18 GPa, diopside dissociates to CaSiO 3-rich perovskite + Mg-rich (Mg,Ca)SiO 3 tetragonal garnet (Gt) above about 1400 °C. The solubilities of CaSiO 3 in garnet and MgSiO 3 in perovskite increase with temperature. At 17-18 GPa below about 1400 °C, diopside dissociates to Ca-perovskite + β-Mg 2SiO 4 + stishovite. The Mg, Si-phases coexisting with Ca-perovskite change to γ-Mg 2SiO 4 + stishovite, to ilmenite, and finally to Mg-perovskite with increasing pressure. CaSiO 3 wollastonite transforms to the walstromite structure, and further dissociates to Ca 2SiO 4 larnite + CaSi 2O 5 titanite. The latter transition occurs at 9-11 GPa with a positive Clapeyron slope. At 1600 °C, larnite + titanite transform to CaSiO 3 perovskite at 14.6±0.6 GPa, calibrated against the α-β transition pressure of Mg 2SiO 4. The enthalpies of formation of CaSiO 3 walstromite and CaSi 2O 5 titanite from the mixture of CaO and SiO 2 quartz at 298 K have been determined as -76.1±2.8, and -27.8±2.1 kJ/mol, respectively. The latter was estimated from enthalpy measurements of titanite solid solutions in the system CaSi 2O 5-CaTiSiO 5, because CaSi 2O 5 titanite transforms to a triclinic phase upon decompression. The enthalpy difference between titanite and the triclinic phase is only 1.5±4.8 kJ/mol. Using these enthalpies of formation and those of larnite and CaSiO 3 perovskite, the transition boundaries in CaSiO 3 have been calculated. The calculated boundaries for the wollastonite-walstromite-larnite + titanite transitions are consistent with the experimental determinations within the errors. The calculated boundary between larnite + titanite and Ca-perovskite has a slope of

Two-photon absorption of KBe2BO3F2 and CsLiB6O10 at 193 nm

NASA Astrophysics Data System (ADS)

Nakazato, Tomoharu; Wang, Xiaoyang; Chen, Chuangtian; Watanabe, Shuntaro

2017-12-01

We measured the two-photon absorption coefficients of KBe2BO3F2 (KBBF) and CsLiB6O10 (CLBO) at 193.5 nm using CaF2 as a reference. This is the first report about KBBF measurement at any wavelength. The two-photon absorption coefficients of KBBF, CLBO, and CaF2 were 1.3 × 10-9, 1.0 × 10-9, and 0.8 × 10-9 cm/W, respectively. We also measured the fluorescence spectra of KBBF, CLBO, and CaF2 excited by 193.5 nm light. The observed spectrum of KBBF had a broad peak at 322 nm, similar to that of CaF2. The luminescence intensity showed a quadratic dependence on incident laser intensity for KBBF and CaF2, indicating a two-photon process, but showed a linear dependence for CLBO. Taken together, we conclude that the two-photon fluorescence of KBBF originates, as in the case of CaF2, from the transition of a self-trapped exciton formed by a F2 - ion (self-trapped hole), which captures an electron.

Atomic intercalation to measure adhesion of graphene on graphite

PubMed Central

Wang, Jun; Sorescu, Dan C.; Jeon, Seokmin; Belianinov, Alexei; Kalinin, Sergei V.; Baddorf, Arthur P.; Maksymovych, Petro

2016-01-01

The interest in mechanical properties of two-dimensional materials has emerged in light of new device concepts taking advantage of flexing, adhesion and friction. Here we demonstrate an effective method to measure adhesion of graphene atop highly ordered pyrolytic graphite, utilizing atomic-scale ‘blisters' created in the top layer by neon atom intercalates. Detailed analysis of scanning tunnelling microscopy images is used to reconstruct atomic positions and the strain map within the deformed graphene layer, and demonstrate the tip-induced subsurface translation of neon atoms. We invoke an analytical model, originally devised for graphene macroscopic deformations, to determine the graphite adhesion energy of 0.221±0.011 J m−2. This value is in excellent agreement with reported macroscopic values and our atomistic simulations. This implies mechanical properties of graphene scale down to a few-nanometre length. The simplicity of our method provides a unique opportunity to investigate the local variability of nanomechanical properties in layered materials. PMID:27796294

Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05268a Click here for additional data file.

PubMed Central

Zhou, Xiuquan; Eckberg, Christopher; Wilfong, Brandon; Liou, Sz-Chian; Vivanco, Hector K.; Paglione, Johnpierre

2017-01-01

Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li1–xFexOH)FeS, [(Na1–xFex)(OH)2]FeS, and KxFe2–yS2. Upon successful intercalation of the FeS layer, the superconducting critical temperature T c of mackinawite is enhanced from 5 K to 8 K for the (Li1–xFexOH)δ+ intercalate. Layered heterostructures of [(Na1–xFex)(OH)2]FeS resemble the natural mineral tochilinite, which contains an iron square lattice interleaved with a hexagonal hydroxide lattice. Whilst heterostructured [(Na1–xFex)(OH)2]FeS displays long-range magnetic ordering near 15 K, KxFe2–yS2 displays short range antiferromagnetism. PMID:28580110

The radioactivity estimation of 14C and 3H in graphite waste samples of the KRR-2.

PubMed

Reyoung Kim, Hee

2013-09-01

The radioactivity of (14)C and (3)H in graphite samples from the dismantled Korea Research Reactor-2 (the KRR-2) site was analyzed by high-temperature oxidation and liquid scintillation counting, and the graphite waste was suggested to be disposed of as a low-level radioactive waste. The graphite samples were oxidized at a high temperature of 800 °C, and their counting rates were measured by using a liquid scintillation counter (LSC). The combustion ratio of the graphite was about 99% on the sample with a maximum weight of 1g. The recoveries from the combustion furnace were around 100% and 90% in (14)C and (3)H, respectively. The minimum detectable activity was 0.04-0.05 Bq/g for the (14)C and 0.13-0.15 Bq/g for the (3)H at the same background counting time. The activity of (14)C was higher than that of (3)H over all samples with the activity ratios of the (14)C to (3)H, (14)C/(3)H, being between 2.8 and 25. The dose calculation was carried out from its radioactivity analysis results. The dose estimation gave a higher annual dose than the domestic legal limit for a clearance. It was thought that the sampled graphite waste from the dismantled research reactor was not available for reuse or recycling and should be monitored as low-level radioactive waste. Copyright © 2013 Elsevier Ltd. All rights reserved.

Li Storage of Calcium Niobates for Lithium Ion Batteries.

PubMed

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

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.

Te/C nanocomposites for Li-Te Secondary Batteries

NASA Astrophysics Data System (ADS)

Seo, Jeong-Uk; Seong, Gun-Kyu; Park, Cheol-Min

2015-01-01

New battery systems having high energy density are actively being researched in order to satisfy the rapidly developing market for longer-lasting mobile electronics and hybrid electric vehicles. Here, we report a new Li-Te secondary battery system with a redox potential of ~1.7 V (vs. Li+/Li) adapted on a Li metal anode and an advanced Te/C nanocomposite cathode. Using a simple concept of transforming TeO2 into nanocrystalline Te by mechanical reduction, we designed an advanced, mechanically reduced Te/C nanocomposite electrode material with high energy density (initial discharge/charge: 1088/740 mA h cm-3), excellent cyclability (ca. 705 mA h cm-3 over 100 cycles), and fast rate capability (ca. 550 mA h cm-3 at 5C rate). The mechanically reduced Te/C nanocomposite electrodes were found to be suitable for use as either the cathode in Li-Te secondary batteries or a high-potential anode in rechargeable Li-ion batteries. We firmly believe that the mechanically reduced Te/C nanocomposite constitutes a breakthrough for the realization and mass production of excellent energy storage systems.

Electrochemical performance of LiNi0.4Co0.2Mn0.4O2 prepared by different molten salt flux: LiNO3-LiCl and LiNO3-KNO3

NASA Astrophysics Data System (ADS)

Satyanarayana, M.; James, Joseph; U. V., Varadaraju

2017-10-01

LiNi0.4Co0.2Mn0.4O2 material synthesized at different temperatures by using LiNO3-LiCl and LiNO3-KNO3 molten salt as a reaction medium. The phase purity of the samples obtained by powder X-ray diffraction measurement which suggests layered α-NaFeO2 type is obtained at 800-900 °C using LiNO3-LiCl flux and at 750-850 °C using LiNO3-KNO3 flux. The surface morphology change with flux media at different temperature are obtained by scanning electron microscopy analysis. The galvanostatic cycling results show that the high stable reversible discharge capacity of 155 (±3) mAh g-1 obtained for treated compound at 900 °C for 1 h (using LiNO3-LiCl) with coloumbic efficiency of 99%. The reversible discharge capacity of 140 and 130 (±3) mAh g-1 obtained for treated compound at 750 and 850 °C, respectively (using LiNO3-KNO3).

Synthesis of Ca(PF6)2, formed via nitrosonium oxidation of calcium.

PubMed

Keyzer, Evan N; Matthews, Peter D; Liu, Zigeng; Bond, Andrew D; Grey, Clare P; Wright, Dominic S

2017-04-20

The development of rechargeable Ca-ion batteries as an alternative to Li systems has been limited by the availability of suitable electrolyte salts. We present the synthesis of complexes of Ca(PF 6 ) 2 (a key potential Ca battery electrolyte salt) via the treatment of Ca metal with NOPF 6 , and explore their conversion to species containing PO 2 F 2 - under the reaction conditions.

Gaussian approximation potential modeling of lithium intercalation in carbon nanostructures

NASA Astrophysics Data System (ADS)

Fujikake, So; Deringer, Volker L.; Lee, Tae Hoon; Krynski, Marcin; Elliott, Stephen R.; Csányi, Gábor

2018-06-01

We demonstrate how machine-learning based interatomic potentials can be used to model guest atoms in host structures. Specifically, we generate Gaussian approximation potential (GAP) models for the interaction of lithium atoms with graphene, graphite, and disordered carbon nanostructures, based on reference density functional theory data. Rather than treating the full Li-C system, we demonstrate how the energy and force differences arising from Li intercalation can be modeled and then added to a (prexisting and unmodified) GAP model of pure elemental carbon. Furthermore, we show the benefit of using an explicit pair potential fit to capture "effective" Li-Li interactions and to improve the performance of the GAP model. This provides proof-of-concept for modeling guest atoms in host frameworks with machine-learning based potentials and in the longer run is promising for carrying out detailed atomistic studies of battery materials.

The 3R polymorph of CaSi{sub 2}

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

Nedumkandathil, Reji; Benson, Daryn E.; Grins, Jekabs

The Zintl phase CaSi{sub 2} commonly occurs in the 6R structure where puckered hexagon layers of Si atoms are stacked in an AA′BB′CC′ fashion. In this study we show that sintering of CaSi{sub 2} in a hydrogen atmosphere (30 bar) at temperatures between 200 and 700 °C transforms 6R-CaSi{sub 2} quantitatively into 3R-CaSi{sub 2}. In the 3R polymorph (space group R-3m (no. 166), a=3.8284(1), c=15.8966(4), Z=3) puckered hexagon layers are stacked in an ABC fashion. The volume per formula unit is about 3% larger compared to 6R-CaSi{sub 2}. First principles density functional calculations reveal that 6R and 3R-CaSi{sub 2} aremore » energetically degenerate at zero Kelvin. With increasing temperature 6R-CaSi{sub 2} stabilizes over 3R because of its higher entropy. This suggests that 3R-CaSi{sub 2} should revert to 6R at elevated temperatures, which however is not observed up to 800 °C. 3R-CaSi{sub 2} may be stabilized by small amounts of incorporated hydrogen and/or defects. - Graphical abstract: The common 6R form of CaSi{sub 2} can be transformed quantitatively into 3R-CaSi{sub 2} upon sintering in a hydrogen atmosphere. - Highlights: • Quantitative and reproducible bulk synthesis of the rare 3R polymorph of CaSi{sub 2}. • Clarification of the energetic relation between 3R and conventional 6R form. • 3R-CaSi{sub 2} is presumably stabilized by small amounts of incorporated hydrogen and/or defects.« less

Structural and Kinetic Properties of Graphite Intercalation Compounds

DTIC Science & Technology

1982-08-21

the case of FeCI3 , and Dowel2 for Br2, HNO3 and PdC 2 have investigated rates of intercalation to determine diffusion coefficients. Bardhan et al.18...Chim. 21, 1312 (1954). 17. T. Sasa, Y. Takahashi and T. Mukaibo, Carbon 9, 407 (1971). 18. K. K. Bardhan and D. D. L. Chung, Carbon 18, 313 (1980). 19...S. H. Anderson and D. D. L. Chung, Ext. Abst. Program -- Bienn. Conf. Carbon 15, 361 (1981). 20. K. K. Bardhan and D. D. L. Chung, Carbon 18, 303

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.

Breathing of Graphite Particles in a Lithium-Ion Battery

NASA Astrophysics Data System (ADS)

Takata, Keiji; Okuda, Mitsuhiro; Yura, Nobuki; Tamura, Ryota

2012-04-01

We imaged changes in volume of graphite particles in a Li-ion battery due to the insertion and extraction of Li ions using scanning probe microscopy. When Li ions were extracted from the graphite particles, the particles were contracted, while expansion was induced in the interspaces between the particles. Variations of the images of volume changes depending on modulation frequencies clearly showed lithium intercalation. A linear relationship between the amplitudes of volume changes and the products of the diffusion elements and the reciprocals of the frequencies has been proven. Thus, the detected signals quantitatively well corresponded to the lithium ion movements.

Powder, paper and foam of few-layer graphene prepared in high yield by electrochemical intercalation exfoliation of expanded graphite.

PubMed

Wu, Liqiong; Li, Weiwei; Li, Peng; Liao, Shutian; Qiu, Shengqiang; Chen, Mingliang; Guo, Yufen; Li, Qi; Zhu, Chao; Liu, Liwei

2014-04-09

A facile and high-yield approach to the preparation of few-layer graphene (FLG) by electrochemical intercalation exfoliation (EIE) of expanded graphite in sulfuric acid electrolyte is reported. Stage-1 H2SO4-graphite intercalation compound is used as a key intermediate in EIE to realize the efficient exfoliation. The yield of the FLG sheets (<7 layers) with large lateral sizes (tens of microns) is more than 75% relative to the total amount of starting expanded graphite. A low degree of oxygen functionalization existing in the prepared FLG flakes enables them to disperse effectively, which contributes to the film-forming characteristics of the FLG flakes. These electrochemically exfoliated FLG flakes are integrated into several kinds of macroscopic graphene structures. Flexible and freestanding graphene papers made of the FLG flakes retain excellent conductivity (≈24,500 S m(-1)). Three-dimensional (3D) graphene foams with light weight are fabricated from the FLG flakes by the use of Ni foams as self-sacrifice templates. Furthermore, 3D graphene/Ni foams without any binders, which are used as supercapacitor electrodes in aqueous electrolyte, provide the specific capacitance of 113.2 F g(-1) at a current density of 0.5 A g(-1), retaining 90% capacitance after 1000 cycles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Electrode behavior RE-visited: Monitoring potential windows, capacity loss, and impedance changes in Li 1.03 (Ni 0.5Co 0.2Mn 0.3) 0.97O 2/silicon-graphite full cells

DOE PAGES

Klett, Matilda; Gilbert, James A.; Trask, Stephen E.; ...

2016-03-04

Here, the capacity and power performance of lithium-ion battery cells evolve over time. The mechanisms leading to these changes can often be identified through knowledge of electrode potentials, which contain information about electrochemical processes at the electrode-electrolyte interfaces. In this study we monitor electrode potentials within full cells containing a Li 1.03(Ni 0.5Co 0.2Mn 0.3) 0.97O 2–based (NCM523) positive electrode, a silicon-graphite negative electrode, and an LiPF6-bearing electrolyte, with and without fluoroethylene carbonate (FEC) or vinylene carbonate (VC) additives. The electrode potentials are monitored with a Li-metal reference electrode (RE) positioned besides the electrode stack; changes in these potentials aremore » used to examine electrode state-of-charge (SOC) shifts, material utilization, and loss of electrochemically active material. Electrode impedances are obtained with a Li xSn RE located within the stack; the data display the effect of cell voltage and electrode SOC changes on the measured values after formation cycling and after aging. Our measurements confirm the beneficial effect of FEC and VC electrolyte additives in reducing full cell capacity loss and impedance rise after cycling in a 3.0–4.2 V range. Comparisons with data from a full cell containing a graphite-based negative highlight the consequences of including silicon in the electrode. Our observations on electrode potentials, capacity, and impedance changes on cycling are crucial to designing long-lasting, silicon-bearing, lithium-ion cells.« less

12CaO-7Al2O3 Electride Hollow Cathode

NASA Technical Reports Server (NTRS)

Williams, John D. (Inventor); Rand, Lauren P. (Inventor); Martinez, Rafael A. (Inventor)

2017-01-01

The use of the electride form of 12CaO-7Al2O3, or C12A7, as a low work function electron emitter in a hollow cathode discharge apparatus is described. No heater is required to initiate operation of the present cathode, as is necessary for traditional hollow cathode devices. Because C12A7 has a fully oxidized lattice structure, exposure to oxygen does not degrade the electride. The electride was surrounded by a graphite liner since it was found that the C12A7 electride converts to it's eutectic (CA+C3A) form when heated (through natural hollow cathode operation) in a metal tube.

Theoretical descriptions of novel triplet germylenes M1-Ge-M2-M3 (M1 = H, Li, Na, K; M2 = Be, Mg, Ca; M3 = H, F, Cl, Br).

PubMed

Kassaee, Mohamad Zaman; Ashenagar, Samaneh

2018-02-06

In a quest to identify new ground-state triplet germylenes, the stabilities (singlet-triplet energy differences, ΔE S-T ) of 96 singlet (s) and triplet (t) M 1 -Ge-M 2 -M 3 species were compared and contrasted at the B3LYP/6-311++G**, QCISD(T)/6-311++G**, and CCSD(T)/6-311++G** levels of theory (M 1  = H, Li, Na, K; M 2  = Be, Mg, Ca; M 3  = H, F, Cl, Br). Interestingly, F-substituent triplet germylenes (M 3  = F) appear to be more stable and linear than the corresponding Cl- or Br-substituent triplet germylenes (M 3  = Cl or Br). Triplets with M 1  = K (i.e., the K-Ge-M 2 -M 3 series) seem to be more stable than the corresponding triplets with M 1  = H, Li, or Na. This can be attributed to the higher electropositivity of potassium. Triplet species with M 3  = Cl behave similarly to those with M 3  = Br. Conversely, triplets with M 3  = H show similar stabilities and linearities to those with M 3  = F. Singlet species of formulae K-Ge-Ca-Cl and K-Ge-Ca-Br form unexpected cyclic structures. Finally, the triplet germylenes M 1 -Ge-M 2 -M 3 become more stable as the electropositivities of the α-substituents (M 1 and M 2 ) and the electronegativity of the β-substituent (M 3 ) increase.

Luminescence characteristics of C5+ ions and 60Co irradiated Li2BaP2O7:Dy3+ phosphor

NASA Astrophysics Data System (ADS)

Wani, J. A.; Dhoble, N. S.; Lochab, S. P.; Dhoble, S. J.

2015-04-01

In this work a study on some thermoluminescence characteristics of Li2BaP2O7:Dy phosphor is presented. The phosphor was synthesized by solid state diffusion method and characterized for its phase purity by X-ray diffraction (XRD). FT-IR spectrum was also carried out to confirm the presence of phosphate family and vibrations corresponding to P-O-P group. Spectroscopic investigation was approached through photoluminescence (PL) and thermoluminescence (TL). PL emission spectrum of Dy3+ ions corresponding to 4F9/2 → 6H13/2 (483 nm) and 4F9/2 → 6H15/2 (574 nm) transitions is revealed under 351 nm excitation wavelength. This characteristic emission confirms the presence of Dy3+ ions in the Li2BaP2O7 host matrix. To induce TL properties in Li2BaP2O7:Dy phosphor was irradiated with C5+ ion beams and gamma rays (60Co). A nearly simple glow curve was observed for Li2BaP2O7:Dy under two different excitation sources. TL response is almost linear over a wide range. Average absorbed dose (D bar) and mean linear energy transfer (LET ‾) of C5+ ion beams in Li2BaP2O7:Dy have also been calculated. Values of parameters like E and S known as trap depth and frequency factor respectively were obtained by using TLanal computer program. Also SRIM based calculations were performed to study the effect of C5+ ion beams on the samples of Li2BaP2O7:Dy. SRIM calculations show that Ba2+ vacancies are highest in number. Till date no such luminescence information on Li2BaP2O7:Dy phosphor is available.

Crystallization behavior of the Li2S-P2S5 glass electrolyte in the LiNi1/3Mn1/3Co1/3O2 positive electrode layer.

PubMed

Tsukasaki, Hirofumi; Mori, Yota; Otoyama, Misae; Yubuchi, So; Asano, Takamasa; Tanaka, Yoshinori; Ohno, Takahisa; Mori, Shigeo; Hayashi, Akitoshi; Tatsumisago, Masahiro

2018-04-18

Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and 75Li 2 S·25P 2 S 5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the β-Li 3 PS 4 precipitated at approximately 200 °C, and then Li 4 P 2 S 6 and Li 2 S precipitated at approximately 400 °C. Because the Li 4 P 2 S 6 and Li 2 S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.

Staging properties of potassium-ammonia ternary graphite intercalation compounds at high ammonia pressure

NASA Astrophysics Data System (ADS)

Qian, X. W.; Solin, S. A.

1989-04-01

The pressure dependence of the (00l) x-ray diffraction patterns of the ternary graphite intercalation compound K(NH3)xC24 has been studied in the range 0.5-11 kbar (for which x~4.5) using a diamond anvil cell. A special apparatus for loading the cell with liquid ammonia at room temperature has been constructed and is briefly described. In these experiments, the pressure-transmitting fluid was also an intercalant, namely ammonia. Therefore, the chemical potential of this species was linearly coupled to the applied pressure in contrast to the usual case where the pressure-transmitting fluid is chemically passive. The pressure dependences of the basal spacings and of the relative intensities of key reflections have been measured, as have the compressibilities of the stage-1 and stage-2 components of the two-phase system. Basal-spacing anomalies and anomalies in the relative intensities occur at pressures of ~3.5 and 8.0 kbar and are tentatively attributed to in-plane coordination changes in the potassium-ammonia ratio. Using thermodynamic arguments and Le Chatelier's principle we show quantitatively that a staging phase transition from pure stage-1 phase to an admixture of stage-1 and stage-2 is expected with increased pressure above 10 bar in agreement with experiment. The saturation ammonia compositions (x values) of the admixed stages are found to be 4.5 and 5.4 for the stage-1 and -2 components, respectively. This result is interpreted as evidence that the composition is not sterically limited but is determined by the binding energy of ammonia for potassium and by the perturbation to this energy from the guest-host interaction.

Complete Decomposition of Li 2 CO 3 in Li–O 2 Batteries Using Ir/B 4 C as Noncarbon-Based Oxygen Electrode

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

Song, Shidong; Xu, Wu; Zheng, Jianming

Incomplete decomposition of Li2CO3 during charge process is a critical barrier for rechargeable Li-O2 batteries. Here we report complete decomposition of Li2CO3 in Li-O2 batteries using ultrafine iridium-decorated boron carbide (Ir/B4C) nanocomposite as oxygen electrode. The systematic investigation on charging the Li2CO3 preloaded Ir/B4C electrode in an ether-based electrolyte demonstrates that Ir/B4C electrode can decompose Li2CO3 with an efficiency close to 100% at below 4.37 V. In contrast, the bare B4C without Ir electrocatalyst can only decompose 4.7% of preloaded Li2CO3. The reaction mechanism of Li2CO3 decomposition in the presence of Ir/B4C electrocatalyst has been further investigated. A Li-O2 batterymore » using Ir/B4C as oxygen electrode material shows highly enhanced cycling stability than that using bare B4C oxygen electrode. These results clearly demonstrate that Ir/B4C is an effecitive oxygen electrode amterial to completely decompose Li2CO3 at relatively low charge voltages and is of significant importance in improving the cycle performanc of aprotic Li-O2 batteries.« less

Li14P2O3N6 and Li7PN4: Computational study of two nitrogen rich crystalline LiPON electrolyte materials

NASA Astrophysics Data System (ADS)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

2017-10-01

Two lithium oxonitridophosphate materials are computationally examined and found to be promising solid electrolytes for possible use in all solid-state batteries having metallic Li anodes - Li14P2O3N6 and Li7PN4. The first principles simulations are in good agreement with the structural analyses reported in the literature for these materials and the computed total energies indicate that both materials are stable with respect to decomposition into binary and ternary products. The computational results suggest that both materials are likely to form metastable interfaces with Li metal. The simulations also find both materials to have Li ion migration activation energies comparable or smaller than those of related Li ion electrolyte materials. Specifically, for Li7PN4, the experimentally measured activation energy can be explained by the migration of a Li ion vacancy stabilized by a small number of O2- ions substituting for N3- ions. For Li14P2O3N6, the activation energy for Li ion migration has not yet been experimentally measured, but simulations predict it to be smaller than that measured for Li7PN4.

Observation of Landau levels in potassium-intercalated graphite under a zero magnetic field

PubMed Central

Guo, Donghui; Kondo, Takahiro; Machida, Takahiro; Iwatake, Keigo; Okada, Susumu; Nakamura, Junji

2012-01-01

The charge carriers in graphene are massless Dirac fermions and exhibit a relativistic Landau-level quantization in a magnetic field. Recently, it has been reported that, without any external magnetic field, quantized energy levels have been also observed from strained graphene nanobubbles on a platinum surface, which were attributed to the Landau levels of massless Dirac fermions in graphene formed by a strain-induced pseudomagnetic field. Here we show the generation of the Landau levels of massless Dirac fermions on a partially potassium-intercalated graphite surface without applying external magnetic field. Landau levels of massless Dirac fermions indicate the graphene character in partially potassium-intercalated graphite. The generation of the Landau levels is ascribed to a vector potential induced by the perturbation of nearest-neighbour hopping, which may originate from a strain or a gradient of on-site potentials at the perimeters of potassium-free domains. PMID:22990864

Conduction below 100 °C in nominal Li 6ZnNb 4O 14

DOE PAGES

Li, Yunchao; Paranthaman, Mariappan Parans; Gill, Lance W.; ...

2015-09-15

The increasing demand for a safe rechargeable battery with a high energy density per cell is driving a search for a novel solid electrolyte with a high Li + or Na + conductivity that is chemically stable in a working Li-ion or Na-ion battery. Li 6ZnNb 4O 14 has been reported to exhibit a σ Li > 10 -2 S cm -1 at 250 °C, but to disproportionate into multiple phases on cooling from 850 °C to room temperature. An investigation of the room-temperature Li-ion conductivity in a porous pellet of a multiphase product of a nominal Li 6ZnNb 4Omore » 14 composition is shown to have bulk σ Li 3.3 x 10 -5 S cm -1 at room temperature that increases to 1.4 x 10 -4 S cm -1 by 50 °C. 7Li MAS NMR spectra were fitted to two Lorentzian lines, one of which showed a dramatic increase with increasing temperature. As a result, a test for water stability indicates that Li + may move to the particle and grain surfaces to react with adsorbed water as occurs in the garnet Li + conductors.« less

Environmentally-friendly oxygen-free roasting/wet magnetic separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent LiCoO2/graphite lithium batteries.

PubMed

Li, Jia; Wang, Guangxu; Xu, Zhenming

2016-01-25

The definite aim of the present paper is to present some novel methods that use oxygen-free roasting and wet magnetic separation to in situ recycle of cobalt, Lithium Carbonate and Graphite from mixed electrode materials. The in situ recycling means to change waste into resources by its own components, which is an idea of "waste+waste→resources." After mechanical scraping the mixed electrode materials enrich powders of LiCoO2 and graphite. The possible reaction between LiCoO2 and graphite was obtained by thermodynamic analysis. The feasibility of the reaction at high temperature was studied with the simultaneous thermogravimetry analysis under standard atmospheric pressure. Then the oxygen-free roasting/wet magnetic separation method was used to transfer the low added value mixed electrode materials to high added value products. The results indicated that, through the serious technologies of oxygen-free roasting and wet magnetic separation, mixture materials consist with LiCoO2 and graphite powders are transferred to the individual products of cobalt, Lithium Carbonate and Graphite. Because there is not any chemical solution added in the process, the cost of treating secondary pollution can be saved. This study provides a theoretical basis for industrial-scale recycling resources from spent LIBs. Copyright © 2015 Elsevier B.V. All rights reserved.

The system Na2CO3-CaCO3 at 3 GPa

NASA Astrophysics Data System (ADS)

Podborodnikov, Ivan V.; Shatskiy, Anton; Arefiev, Anton V.; Rashchenko, Sergey V.; Chanyshev, Artem D.; Litasov, Konstantin D.

2018-04-01

It was suggested that alkali-alkaline earth carbonates may have a substantial role in petrological processes relevant to metasomatism and melting of the Earth's mantle. Because natrite, Na2CO3, Na-Ca carbonate (shortite and/or nyerereite), and calcite, CaCO3, have been recently reported from xenoliths of shallow mantle (110-115 km) origin, we performed experiments on phase relations in the system Na2CO3-CaCO3 at 3 GPa and 800-1300 °C. We found that the system has one intermediate compound, Na2Ca3(CO3)4, at 800 °C, and two intermediate compounds, Na2Ca(CO3)2 and Na2Ca3(CO3)4, at 850 °C. CaCO3 crystals recovered from experiments at 950 and 1000 °C are aragonite and calcite, respectively. Maximum solid solution of CaCO3 in Na2CO3 is 20 mol% at 850 °C. The Na-carbonate-Na2Ca(CO3)2 eutectic locates near 860 °C and 56 mol% Na2CO3. Na2Ca(CO3)2 melts incongruently near 880 °C to produce Na2Ca3(CO3)4 and a liquid containing about 51 mol% Na2CO3. Na2Ca3(CO3)4 disappears above 1000 °C via incongruent melting to calcite and a liquid containing about 43 mol% Na2CO3. At 1050 °C, the liquid, coexisting with Na-carbonate, contains 87 mol% Na2CO3. Na-carbonate remains solid up to 1150 °C and melts at 1200 °C. The Na2CO3 content in the liquid coexisting with calcite decreases to 15 mol% as temperature increases to 1300 °C. Considering the present and previous data, a range of the intermediate compounds on the liquidus of the Na2CO3-CaCO3 join changes as pressure increases in the following sequence: Na2Ca(CO3)2 (0.1 GPa) → Na2Ca(CO3)2, Na2Ca3(CO3)4 (3 GPa) → Na4Ca(CO3)3, Na2Ca3(CO3)4 (6 GPa). Thus, the Na2Ca(CO3)2 nyerereite stability field extends to the shallow mantle pressures. Consequently, findings of nyerereite among daughter phases in the melt inclusions in olivine from the sheared garnet peridotites are consistent with their mantle origin.

High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

PubMed

Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

2016-07-21

In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

Ansa-Complexes of [Mn(η(5) -C5 H5 )(η(6) -C6 H6 )]: Preparation, Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3).

PubMed

Braunschweig, Holger; Damme, Alexander; Dück, Klaus; Fuß, Marco; Hörl, Christian; Kramer, Thomas; Krummenacher, Ivo; Kupfer, Thomas; Paprocki, Valerie; Schneider, Christoph

2015-10-12

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa-bridging elements. Their preparation was achieved by salt-elimination reactions of the dilithiated precursor [Mn(η(5) -C5 H4 Li)(η(6) -C6 H5 Li)]⋅pmdta (pmdta=N,N,N',N',N''-pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single-atom-bridged derivatives, [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] and [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SiPh2 ], could also be determined by X-ray structural analysis. We investigated for the first time the reactivity of these ansa-cyclopentadienyl-benzene manganese compounds. The reaction of the distannyl-bridged complex [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )Sn2 tBu4 ] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn-Sn bond to give a triatomic ansa-bridge. The investigation of the ring-opening polymerization (ROP) capability of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] with [Pt(PEt3 )3 ] showed that an unexpected, unselective insertion into the Cipso -Sn bonds of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] had occurred. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Li3Ge3Se6: the first ternary lithium germanium selenide with interesting ∞[Ge6Se12]n chains constructed by ethane-like [Ge2Se6]6- clusters.

PubMed

Li, Guangmao; Zhen, Ni; Chu, Yu; Zhou, Zhongxiang

2017-12-21

Li 3 Ge 3 Se 6 , the first compound of the ternary Li/Ge/Se system, has been synthesized. Note that interesting 1D ∞ [Ge 6 Se 12 ] n chains constructed by ethane-like [Ge 2 Se 6 ] 6- clusters were discovered in its structure. Investigations on the structures of all the [Ge 2 Se 6 ] 6- cluster-containing compounds have shown that only in Li 3 Ge 3 Se 6 are there 1D chains composed of [Ge 2 Se 6 ] 6- clusters, which result from the space limitation within the tunnels surrounded by LiSe 6 octahedra. Raman spectrum was obtained to demonstrate the existence of Ge-Ge bonds. UV-visible-NIR diffuse reflection spectrum showed an optical bandgap of 2.08 eV. Theoretical calculations based on first principles have also been performed for its band structure and density of states to analyze its structure-property relationship.

Li induced effects in the core level and π-band electronic structure of graphene grown on C-face SiC

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

Johansson, Leif I., E-mail: lij@ifm.liu.se; Xia, Chao; Virojanadara, Chariya

Studies of the effects induced in the electronic structure after Li deposition, and subsequent heating, on graphene samples prepared on C-face SiC are reported. The as prepared graphene samples are essentially undoped, but after Li deposition, the Dirac point shifts down to 1.2 eV below the Fermi level due to electron doping. The shape of the C 1s level also indicates a doping concentration of around 10{sup 14 }cm{sup −2} after Li deposition, when compared with recent calculated results of core level spectra of graphene. The C 1s, Si 2p, and Li 1s core level results show little intercalation directly after depositionmore » but that most of the Li has intercalated after heating at 280 °C. Heating at higher temperatures leads to desorption of Li from the sample, and at 1030 °C, Li can no longer be detected on the sample. The single π-band observable from multilayer C-face graphene samples in conventional angle resolved photoelectron spectroscopy is reasonably sharp both on the initially prepared sample and after Li deposition. After heating at 280 °C, the π-band appears more diffuse and possibly split. The Dirac point becomes located at 0.4 eV below the Fermi level, which indicates occurrence of a significant reduction in the electron doping concentration. Constant energy photoelectron distribution patterns extracted from the as prepared graphene C-face sample and also after Li deposition and heating at 280 °C look very similar to earlier calculated distribution patterns for monolayer graphene.« less

Efficient rare-earth free red-emitting Ca2YSbO6:Mn4+,M(M = Li+, Na+, K+, Mg2+) phosphors for white light-emitting diodes.

PubMed

Zhong, Jiasong; Chen, Daqin; Chen, Xiao; Wang, Keyuan; Li, Xinyue; Zhu, Yiwen; Ji, Zhenguo

2018-05-08

Owing to its low-cost and satisfactory luminescent-emission performance in warm white light-emitting diodes (w-LEDs), the non-rare-earth Mn4+-activated red phosphor has become a promising competitor of commercial rare-earth doped phosphor. In this study, a series of novel red-light emitting phosphors based on Ca2YSbO6:Mn4+ have been developed successfully by a conventional solid-state reaction. The structural and luminescent properties of these phosphors are systematically investigated. The as-prepared Ca2YSbO6:Mn4+ product exhibits a broad excitation band ranging from 250 to 600 nm and an abnormal intense deep-red emission centered at 680 nm with a full width at half maximum (FWHM) of ∼46 nm. The optimal Mn4+ doping concentration is about 0.3 mol%, and the concentration quenching mechanism is determined to be a dipole-dipole interaction. Impressively, the Ca2YSbO6:0.003Mn4+ phosphor shows an outstanding quantum efficiency of 62.6% and an excellent thermal stability. In addition, the effect of Li+, Mg2+, Na+ and K+ dopants on the luminescent properties of Mn4+-doped Ca2YSbO6 phosphors is elucidated. Furthermore, by employing the as-prepared Ca2YSbO6:Mn4+ as a red component, a warm w-LED with high color rendering index (Ra = 87.5) and low correlated color temperature (CCT = 3255 K) can be acquired. It is believed that the present phosphor has a potential application as a supplement of the red component for warm w-LEDs.

Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

PubMed

Sun, Yige; Tang, Jie; Zhang, Kun; Yuan, Jinshi; Li, Jing; Zhu, Da-Ming; Ozawa, Kiyoshi; Qin, Lu-Chang

2017-02-16

Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g -1 , which is about three times of 372 mA h g -1 , the value expected for the LiC 6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.

Comparing aging of graphite/LiFePO4 cells at 22 °C and 55 °C - Electrochemical and photoelectron spectroscopy studies

NASA Astrophysics Data System (ADS)

Hellqvist Kjell, Maria; Malmgren, Sara; Ciosek, Katarzyna; Behm, Mårten; Edström, Kristina; Lindbergh, Göran

2013-12-01

Accelerated aging at elevated temperature is commonly used to test lithium-ion battery lifetime, but the effect of an elevated temperature is still not well understood. If aging at elevated temperature would only be faster, but in all other respects equivalent to aging at ambient temperature, cells aged to end-of-life (EOL) at different temperatures would be very similar. The present study compares graphite/LiFePO4-based cells either cycle- or calendar-aged to EOL at 22 °C and 55 °C. Cells cycled at the two temperatures show differences in electrochemical impedance spectra as well as in X-ray photoelectron spectroscopy (XPS) spectra. These results show that lithium-ion cell aging is a complex set of processes. At elevated temperature, the aging is accelerated in process-specific ways. Furthermore, the XPS results of cycle-aged samples indicate increased deposition of oxygenated LiPF6 decomposition products in both the negative and positive electrode/electrolyte interfaces. The decomposition seems more pronounced at elevated temperature, and largely accelerated by cycling, which could contribute to the observed cell impedance increase.

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.

Thermal and electrochemical behaviour of C/Li xCoO 2 cell during safety test

NASA Astrophysics Data System (ADS)

Doh, Chil-Hoon; Kim, Dong-Hun; Kim, Hyo-Suck; Shin, Hye-Min; Jeong, Young-Dong; Moon, Seong-In; Jin, Bong-Soo; Eom, Seung Wook; Kim, Hyun-Soo; Kim, Ki-Won; Oh, Dae-Hee; Veluchamy, Angathevar

Thermal and electrochemical processes in a 1000 mAh lithium-ion pouch cell with a graphite anode and a Li xCoO 2 cathode during a safety test are examined. In overcharge tests, the forced current shifts the cell voltage to above 4.2 V. This causes a cell charged at the 1 C rate to lose cycleability and a cell charged at the 3 C rate to undergo explosion. In nail penetration and impact tests, a high discharge current passing through the cells gives rise to thermal runaway. These overcharge and high discharge currents promote joule heat within the cells and leads to decomposition and release of oxygen from the de-lithiated Li xCoO 2 and combustion of carbonaceous materials. X-ray diffraction analysis reveals the presence of Co 3O 4 in the cathode material of a 4.5 V cell heated to 400 °C. The major cathode product formed after the combustion process cells abused by forced current is Co 3O 4 and by discharge current the products are LiCoO 2 and Co 3O 4. The formation of a trace quantity of CoO through the reduction of Co 3O 4 by virtue of the reducing power of the organic solvent is also discussed.

Dual-Layer Oxidation-Protective Plasma-Sprayed SiC-ZrB2/Al2O3-Carbon Nanotube Coating on Graphite

NASA Astrophysics Data System (ADS)

Ariharan, S.; Sengupta, Pradyut; Nisar, Ambreen; Agnihotri, Ankur; Balaji, N.; Aruna, S. T.; Balani, Kantesh

2017-02-01

Graphite is used in high-temperature gas-cooled reactors because of its outstanding irradiation performance and corrosion resistance. To restrict its high-temperature (>873 K) oxidation, atmospheric-plasma-sprayed SiC-ZrB2-Al2O3-carbon nanotube (CNT) dual-layer coating was deposited on graphite substrate in this work. The effect of each layer was isolated by processing each component of the coating via spark plasma sintering followed by isothermal kinetic studies. Based on isothermal analysis and the presence of high residual thermal stress in the oxide scale, degradation appeared to be more severe in composites reinforced with CNTs. To avoid the complexity of analysis of composites, the high-temperature activation energy for oxidation was calculated for the single-phase materials only, yielding values of 11.8, 20.5, 43.5, and 4.5 kJ/mol for graphite, SiC, ZrB2, and CNT, respectively, with increased thermal stability for ZrB2 and SiC. These results were then used to evaluate the oxidation rate for the composites analytically. This study has broad implications for wider use of dual-layer (SiC-ZrB2/Al2O3) coatings for protecting graphite crucibles even at temperatures above 1073 K.

Reversible superconductor-insulator transition in LiTi2O4 induced by Li-ion electrochemical reaction