Science.gov

Sample records for li3v2po43 cathode materials

  1. Cathode material for electrochemical cells

    SciTech Connect

    Ryan, D.M.

    1993-08-24

    A primary cell is described having an anode material, an electrolyte material and a cathode material, wherein said cathode material, in the predischarge condition thereof, is K[sub 3]V[sub 5]O[sub 14].

  2. Cathode materials review

    SciTech Connect

    Daniel, Claus Mohanty, Debasish Li, Jianlin Wood, David L.

    2014-06-16

    The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403-431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead-acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide-hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J. Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783-789) demonstrated a high-energy and high-power LiCoO{sub 2} cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.

  3. Cathode materials review

    NASA Astrophysics Data System (ADS)

    Daniel, Claus; Mohanty, Debasish; Li, Jianlin; Wood, David L.

    2014-06-01

    The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403-431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead-acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide-hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J. Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783-789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.

  4. Cathode material for lithium batteries

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2013-07-23

    A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

  5. Cathode material for lithium batteries

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2015-01-13

    A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

  6. Pyrite cathode material for a thermal battery

    NASA Astrophysics Data System (ADS)

    Pemsler, J. P.; Litchfield, J. K.

    1991-02-01

    The present invention relates in general to a synthetic cathode material for a molten salt battery and, more particularly, to a process of providing and using synthetic pyrite for use as a cathode in a thermal battery. These batteries, which have been successfully used in a number of military applications, include iron disulfide cathode material obtained as benefacted or from natural occurring pyrite deposits, or as a byproduct of flotation concentrate from the processing of base or noble metal ores.

  7. Phthalocyanine cathode materials for secondary lithium cells

    SciTech Connect

    Tamaki, J.; Yamaji, A.

    1982-01-01

    Discharge and charge characteristics of various phthalocyanine cathodes coupled with lithium metal are studied. The best capacity based only on cathode active material weight is 1440 A-hr/kg in the lithium/iron phthalocyanine system, and the cycle life of the lithium/Cu phthalocyanine system is more than 100 times at the discharge depth of 157 A-hr/kg. The cathode reaction mechanism is supposed to be lithium intercalation between phthalocyanine molecules. The results indicate that these phthalocyanines are promising cathode active materials for lithium secondary batteries.

  8. Cells having cathodes containing polycarbon disulfide materials

    DOEpatents

    Okamoto, Yoshi; Skotheim, Terje A.; Lee, Hung S.

    1995-08-15

    The present invention relates to an electric current producing cell which contains an anode, a cathode having as a cathode-active material one or more carbon-sulfur compounds of the formula (CS.sub.x).sub.n, in which x takes values from 1.2 to 2.3 and n is greater or equal to 2, and where the redox process does not involve polymerization and de-polymerization by forming and breaking S--S bonds in the polymer backbone. The cell also contains an electrolyte which is chemically inert with respect to the anode and the cathode.

  9. Cells having cathodes containing polycarbon disulfide materials

    DOEpatents

    Okamoto, Y.; Skotheim, T.A.; Lee, H.S.

    1995-08-15

    The present invention relates to an electric current producing cell which contains an anode, a cathode having as a cathode-active material one or more carbon-sulfur compounds of the formula (CS{sub x}){sub n}, in which x takes values from 1.2 to 2.3 and n is greater or equal to 2, and where the redox process does not involve polymerization and de-polymerization by forming and breaking S--S bonds in the polymer backbone. The cell also contains an electrolyte which is chemically inert with respect to the anode and the cathode. 5 figs.

  10. 2013 Estorm - Invited Paper - Cathode Materials Review

    SciTech Connect

    Daniel, Claus; Mohanty, Debasish; Li, Jianlin; Wood III, David L

    2014-01-01

    The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403 431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783 789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.

  11. Improved cathode materials for microbial electrosynthesis

    SciTech Connect

    Zhang, T; Nie, HR; Bain, TS; Lu, HY; Cui, MM; Snoeyenbos-West, OL; Franks, AE; Nevin, KP; Russell, TP; Lovley, DR

    2013-01-01

    Microbial electrosynthesis is a promising strategy for the microbial conversion of carbon dioxide to transportation fuels and other organic commodities, but optimization of this process is required for commercialization. Cathodes which enhance electrode-microbe electron transfer might improve rates of product formation. To evaluate this possibility, biofilms of Sporomusa ovata, which are effective in acetate electrosynthesis, were grown on a range of cathode materials and acetate production was monitored over time. Modifications of carbon cloth that resulted in a positive-charge enhanced microbial electrosynthesis. Functionalization with chitosan or cyanuric chloride increased acetate production rates 6-7 fold and modification with 3-aminopropyltriethoxysilane gave rates 3-fold higher than untreated controls. A 3-fold increase in electrosynthesis over untreated carbon cloth cathodes was also achieved with polyaniline cathodes. However, not all strategies to provide positively charged surfaces were successful, as treatment of carbon cloth with melamine or ammonia gas did not stimulate acetate electrosynthesis. Treating carbon cloth with metal, in particular gold, palladium, or nickel nanoparticles, also promoted electrosynthesis, yielding electrosynthesis rates that were 6-,4.7- or 4.5-fold faster than the untreated control, respectively. Cathodes comprised of cotton or polyester fabric treated with carbon nanotubes yielded cathodes that supported acetate electrosynthesis rates that were similar to 3-fold higher than carbon cloth controls. Recovery of electrons consumed in acetate was similar to 80% for all materials. The results demonstrate that one approach to increase rates of carbon dioxide reduction in microbial electrosynthesis is to modify cathode surfaces to improve microbe-electrode interactions.

  12. Organic Cathode Materials for Rechargeable Batteries

    SciTech Connect

    Cao, Ruiguo; Qian, Jiangfeng; Zhang, Jiguang; Xu, Wu

    2015-06-28

    This chapter will primarily focus on the advances made in recent years and specify the development of organic electrode materials for their applications in rechargeable lithium batteries, sodium batteries and redox flow batteries. Four various organic cathode materials, including conjugated carbonyl compounds, conducting polymers, organosulfides and free radical polymers, are introduced in terms of their electrochemical performances in these three battery systems. Fundamental issues related to the synthesis-structure-activity correlations, involved work principles in energy storage systems, and capacity fading mechanisms are also discussed.

  13. Nanostructured cathode materials for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Myung, Seung-Taek; Amine, Khalil; Sun, Yang-Kook

    2015-06-01

    The prospect of drastic climate change and the ceaseless fluctuation of fossil fuel prices provide motivation to reduce the use of fossil fuels and to find new energy conversion and storage systems that are able to limit carbon dioxide generation. Among known systems, lithium-ion batteries are recognized as the most appropriate energy storage system because of their high energy density and thus space saving in applications. Introduction of nanotechnology to electrode material is beneficial to improve the resulting electrode performances such as capacity, its retention, and rate capability. The nanostructure is highly available not only when used alone but also is more highlighted when harmonized in forms of core-shell structure and composites with carbon nanotubes, graphene or reduced graphene oxides. This review covers syntheses and electrochemical properties of nanoscale, nanosized, and nanostructured cathode materials for rechargeable lithium batteries.

  14. Chromium (V) compounds as cathode material in electrochemical power sources

    DOEpatents

    Delnick, Frank M.; Guidotti, Ronald A.; McCarthy, David K.

    1985-01-01

    A cathode for use in a thermal battery, comprising a chromium (V) compound. The preferred materials for this use are Ca.sub.5 (CrO.sub.4).sub.3 Cl, Ca.sub.5 (CrO.sub.4).sub.3 OH, and Cr.sub.2 O.sub.5. The chromium (V) compound can be employed as a cathode material in ambient temperature batteries when blended with a suitably conductive filler, preferably carbon black.

  15. Chromium (V) compounds as cathode material in electrochemical power sources

    DOEpatents

    Delnick, F.M.; Guidotti, R.A.; McCarthy, D.K.

    A cathode for use in a thermal battery, comprising a chromium (V) compound. The preferred materials for this use are Ca/sub 5/(CrO/sub 4/)/sub 3/Cl, Ca/sub 5/(CrO/sub 4/)OH, and Cr/sub 2/O/sub 5/. The chromium (V) compound can be employed as a cathode material in ambient temperature batteries when blended with a suitably conductive filler, preferably carbon black.

  16. Durability and performance optimization of cathode materials for fuel cells

    NASA Astrophysics Data System (ADS)

    Colon-Mercado, Hector Rafael

    The primary objective of this dissertation is to develop an accelerated durability test (ADT) for the evaluation of cathode materials for fuel cells. The work has been divided in two main categories, namely high temperature fuel cells with emphasis on the Molten Carbonate Fuel Cell (MCFC) cathode current collector corrosion problems and low temperature fuel cells in particular Polymer Electrolyte Fuel Cell (PEMFC) cathode catalyst corrosion. The high operating temperature of MCFC has given it benefits over other fuel cells. These include higher efficiencies (>50%), faster electrode kinetics, etc. At 650°C, the theoretical open circuit voltage is established, providing low electrode overpotentials without requiring any noble metal catalysts and permitting high electrochemical efficiency. The waste heat is generated at sufficiently high temperatures to make it useful as a co-product. However, in order to commercialize the MCFC, a lifetime of 40,000 hours of operation must be achieved. The major limiting factor in the MCFC is the corrosion of cathode materials, which include cathode electrode and cathode current collector. In the first part of this dissertation the corrosion characteristics of bare, heat-treated and cobalt coated titanium alloys were studied using an ADT and compared with that of state of the art current collector material, SS 316. PEMFCs are the best choice for a wide range of portable, stationary and automotive applications because of their high power density and relatively low-temperature operation. However, a major impediment in the commercialization of the fuel cell technology is the cost involved due to the large amount of platinum electrocatalyst used in the cathode catalyst. In an effort to increase the power and decrease the cathode cost in polymer electrolyte fuel cell (PEMFC) systems, Pt-alloy catalysts were developed to increase its activity and stability. Extensive research has been conducted in the area of new alloy development and

  17. Electrosprayed polyaniline as cathode material for lithium secondary batteries

    SciTech Connect

    Manuel, James; Raghavan, Prasanth; Shin, Chorong; Heo, Min-Yeong; Ahn, Jou-Hyeon; Noh, Jung-Pil; Cho, Gyu-Bong; Ryu, Ho-Suk; Ahn, Hyo-Jun

    2010-03-15

    Doped polyaniline with LiPF{sub 6} is electrosprayed onto aluminum foil using electrospinning technique, and evaluated as cathode active material for application in room-temperature lithium batteries. Doping level is characterized using FTIR and UV-vis spectroscopy. In FTIR Spectra, characteristic peaks of PANI are shifted to lower bands as a result of doping which indicates the effectiveness of doping. Doping level is also confirmed by UV-vis spectra. Surface morphology of the cathode is studied using scanning electron microscope. Electrochemical evaluation of the cell using electrosprayed PANI as cathode show good cycling properties. The cell delivers a high discharge value of 142.5 mAh/g which is about 100% of theoretical capacity, and the capacity is lowered during cycle and reached 61% of theoretical capacity after 50 cycles. The cell delivers a stable but lower discharge capacity at higher C-rates.

  18. Process for Low Cost Domestic Production of LIB Cathode Materials

    SciTech Connect

    Thurston, Anthony

    2012-10-31

    The objective of the research was to determine the best low cost method for the large scale production of the Nickel-Cobalt-Manganese (NCM) layered cathode materials. The research and development focused on scaling up the licensed technology from Argonne National Laboratory in BASF’s battery material pilot plant in Beachwood Ohio. Since BASF did not have experience with the large scale production of the NCM cathode materials there was a significant amount of development that was needed to support BASF’s already existing research program. During the three year period BASF was able to develop and validate production processes for the NCM 111, 523 and 424 materials as well as begin development of the High Energy NCM. BASF also used this time period to provide free cathode material samples to numerous manufactures, OEM’s and research companies in order to validate the ma-terials. The success of the project can be demonstrated by the construction of the production plant in Elyria Ohio and the successful operation of that facility. The benefit of the project to the public will begin to be apparent as soon as material from the production plant is being used in electric vehicles.

  19. High-Capacity, High-Voltage Composite Oxide Cathode Materials

    NASA Technical Reports Server (NTRS)

    Hagh, Nader M.

    2015-01-01

    This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

  20. Olivine Composite Cathode Materials for Improved Lithium Ion Battery Performance

    SciTech Connect

    Ward, R.M.; Vaughey, J.T.

    2006-01-01

    Composite cathode materials in lithium ion batteries have become the subject of a great amount of research recently as cost and safety issues related to LiCoO2 and other layered structures have been discovered. Alternatives to these layered materials include materials with the spinel and olivine structures, but these present different problems, e.g. spinels have low capacities and cycle poorly at elevated temperatures, and olivines exhibit extremely low intrinsic conductivity. Previous work has shown that composite structures containing spinel and layered materials have shown improved electrochemical properties. These types of composite structures have been studied in order to evaluate their performance and safety characteristics necessary for use in lithium ion batteries in portable electronic devices, particularly hybrid-electric vehicles. In this study, we extended that work to layered-olivine and spinel-olivine composites. These materials were synthesized from precursor salts using three methods: direct reaction, ball-milling, and a coreshell synthesis method. X-ray diffraction spectra and electrochemical cycling data show that the core-shell method was the most successful in forming the desired products. The electrochemical performance of the cells containing the composite cathodes varied dramatically, but the low overpotential and reasonable capacities of the spinel-olivine composites make them a promising class for the next generation of lithium ion battery cathodes.

  1. Novel Composite Materials for SOFC Cathode-Interconnect Contact

    SciTech Connect

    J. H. Zhu

    2009-07-31

    This report summarized the research efforts and major conclusions of our University Coal Research Project, which focused on developing a new class of electrically-conductive, Cr-blocking, damage-tolerant Ag-perovksite composite materials for the cathode-interconnect contact of intermediate-temperature solid oxide fuel cell (SOFC) stacks. The Ag evaporation rate increased linearly with air flow rate initially and became constant for the air flow rate {ge} {approx} 1.0 cm {center_dot} s{sup -1}. An activation energy of 280 KJ.mol{sup -1} was obtained for Ag evaporation in both air and Ar+5%H{sub 2}+3%H{sub 2}O. The exposure environment had no measurable influence on the Ag evaporation rate as well as its dependence on the gas flow rate, while different surface morphological features were developed after thermal exposure in the oxidizing and reducing environments. Pure Ag is too volatile at the SOFC operating temperature and its evaporation rate needs to be reduced to facilitate its application as the cathode-interconnect contact. Based on extensive evaporation testing, it was found that none of the alloying additions reduced the evaporation rate of Ag over the long-term exposure, except the noble metals Au, Pt, and Pd; however, these noble elements are too expensive to justify their practical use in contact materials. Furthermore, the addition of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSM) into Ag to form a composite material also did not significantly modify the Ag evaporation rate. The Ag-perovskite composites with the perovskite being either (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.8}Fe{sub 0.2})O{sub 3} (LSCF) or LSM were systematically evaluated as the contact material between the ferritic interconnect alloy Crofer 22 APU and the LSM cathode. The area specific resistances (ASRs) of the test specimens were shown to be highly dependent on the volume percentage and the type of the perovskite present in the composite contact material as well as the amount of thermal cycling

  2. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Allan J. Jacobson

    2006-06-30

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode-electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. In this report, further measurements of the oxygen deficient double perovskite PrBaCo{sub 2}O{sub 5.5+{delta}} are reported. The high electronic conductivity and rapid diffusion and surface exchange kinetics of PBCO suggest its application as cathode material in intermediate temperature solid oxide fuel cells. Preliminary measurements in symmetric cells have shown low ASR values at 600 C. Here we describe the first complete cell measurements on Ni/CGO/CGO/PBCO/CGO cells.

  3. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Allan J. Jacobson

    2005-11-17

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode--electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. In this report, the oxygen exchange kinetics of a P2 composition are described in detail. The oxygen exchange kinetics of the oxygen deficient double perovskite LnBaCo{sub 2}O{sub 5.5+{delta}} (Ln=Pr and Nd) have been determined by electrical conductivity relaxation. The high electronic conductivity and rapid diffusion and surface exchange kinetics of PBCO suggest its application as cathode material in intermediate temperature solid oxide fuel cells.

  4. Material and Energy Flows in the Production of Cathode and Anode Materials for Lithium Ion Batteries

    SciTech Connect

    Dunn, Jennifer B.; James, Christine; Gaines, Linda; Gallagher, Kevin; Dai, Qiang; Kelly, Jarod C.

    2015-09-01

    The Greenhouse gases, Regulated Emissions and Energy use in Transportation (GREET) model has been expanded to include four new cathode materials that can be used in the analysis of battery-powered vehicles: lithium nickel cobalt manganese oxide (LiNi0.4Co0.2Mn0.4O2 [NMC]), lithium iron phosphate (LiFePO4 [LFP]), lithium cobalt oxide (LiCoO2 [LCO]), and an advanced lithium cathode (0.5Li2MnO3∙0.5LiNi0.44Co0.25Mn0.31O2 [LMR-NMC]). In GREET, these cathode materials are incorporated into batteries with graphite anodes. In the case of the LMR-NMC cathode, the anode is either graphite or a graphite-silicon blend. Lithium metal is also an emerging anode material. This report documents the material and energy flows of producing each of these cathode and anode materials from raw material extraction through the preparation stage. For some cathode materials, we considered solid state and hydrothermal preparation methods. Further, we used Argonne National Laboratory’s Battery Performance and Cost (BatPaC) model to determine battery composition (e.g., masses of cathode, anode, electrolyte, housing materials) when different cathode materials were used in the battery. Our analysis concluded that cobalt- and nickel-containing compounds are the most energy intensive to produce.

  5. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Allan J. Jacobson

    2004-07-23

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode - electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. The initial choices for study are perovskite oxides based on Sr substituted LaFeO{sub 3}, where significant data in single cell tests exists at PNNL for cathodes on both YSZ and CSO/YSZ, and Ln{sub 2}NiO{sub 4} compositions. A key component of the research strategy is to evaluate for each cathode material composition, the key performance parameters, including ionic and electronic conductivity, surface exchange rates, stability with respect to the specific electrolyte choice, and thermal expansion coefficients. Results on electrical conductivity relaxation measurements on additional compositions in the La{sub 2}NiO{sub 4+x} and Pr{sub 2}NiO{sub 4+x} series are presented in this report. Studies of the inter-diffusion of amorphous SrFeO{sub 3-x} and LaFeO{sub 3-x} bilayer films prepared by pulsed laser deposition are described. Such studies are a

  6. NANOWIRE CATHODE MATERIAL FOR LITHIUM-ION BATTERIES

    SciTech Connect

    John Olson, PhD

    2004-07-21

    This project involved the synthesis of nanowire ã-MnO2 and characterization as cathode material for high-power lithium-ion batteries for EV and HEV applications. The nanowire synthesis involved the edge site decoration nanowire synthesis developed by Dr. Reginald Penner at UC Irvine (a key collaborator in this project). Figure 1 is an SEM image showing ã-MnO2 nanowires electrodeposited on highly oriented pyrolytic graphite (HOPG) electrodes. This technique is unique to other nanowire template synthesis techniques in that it produces long (>500 um) nanowires which could reduce or eliminate the need for conductive additives due to intertwining of fibers. Nanowire cathode for lithium-ion batteries with surface areas 100 times greater than conventional materials can enable higher power batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs). The synthesis of the ã-MnO2 nanowires was successfully achieved. However, it was not found possible to co-intercalate lithium directly in the nanowire synthesis. Based on input from proposal reviewers, the scope of the project was altered to attempt the conversion into spinel LiMn2O4 nanowire cathode material by solid state reaction of the ã-MnO2 nanowires with LiNO3 at elevated temperatures. Attempts to perform the conversion on the graphite template were unsuccessful due to degradation of the graphite apparently caused by oxidative attack by LiNO3. Emphasis then shifted to quantitative removal of the nanowires from the graphite, followed by the solid state reaction. Attempts to quantitatively remove the nanowires by several techniques were unsatisfactory due to co-removal of excess graphite or poor harvesting of nanowires. Intercalation of lithium into ã-MnO2 electrodeposited onto graphite was demonstrated, showing a partial demonstration of the ã-MnO2 material as a lithium-ion battery cathode material. Assuming the issues of nanowires removal can be solved, the technique does offer potential for creating

  7. Apparatus and method for treating a cathode material provided on a thin-film substrate

    DOEpatents

    Hanson, Eric J.; Kooyer, Richard L.

    2001-01-01

    An apparatus and method for treating a cathode material provided on a surface of a continuous thin-film substrate and a treated thin-film cathode having increased smoothness are disclosed. A web of untreated cathode material is moved between a feed mechanism and a take-up mechanism, and passed through a treatment station. The web of cathode material typically includes areas having surface defects, such as prominences extending from the surface of the cathode material. The surface of the cathode material is treated with an abrasive material to reduce the height of the prominences so as to increase an 85 degree gloss value of the cathode material surface by at least approximately 10. The web of cathode material may be subjected to a subsequent abrasive treatment at the same or other treatment station. Burnishing or lapping film is employed at a treatment station to process the cathode material. An abrasive roller may alternatively be used to process the web of cathode material. The apparatus and method of the present invention may also be employed to treat the surface of a lithium anode foil so as to cleanse and reduce the roughness of the anode foil surface.

  8. Apparatus and method for treating a cathode material provided on a thin-film substrate

    DOEpatents

    Hanson, Eric J.; Kooyer, Richard L.

    2003-01-01

    An apparatus and method for treating a cathode material provided on a surface of a continuous thin-film substrate and a treated thin-film cathode having increased smoothness are disclosed. A web of untreated cathode material is moved between a feed mechanism and a take-up mechanism, and passed through a treatment station. The web of cathode material typically includes areas having surface defects, such as prominences extending from the surface of the cathode material. The surface of the cathode material is treated with an abrasive material to reduce the height of the prominences so as to increase an 85 degree gloss value of the cathode material surface by at least approximately 10. The web of cathode material may be subjected to a subsequent abrasive treatment at the same or other treatment station. Burnishing or lapping film is employed at a treatment station to process the cathode material. An abrasive roller may alternatively be used to process the web of cathode material. The apparatus and method of the present invention may also be employed to treat the surface of a lithium anode foil so as to cleanse and reduce the roughness of the anode foil surface.

  9. Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells.

    PubMed

    Kim, Junyoung; Sengodan, Sivaprakash; Kwon, Goeun; Ding, Dong; Shin, Jeeyoung; Liu, Meilin; Kim, Guntae

    2014-10-01

    We report on an excellent anode-supported H(+) -SOFC material system using a triple conducting (H(+) /O(2-) /e(-) ) oxide (TCO) as a cathode material for H(+) -SOFCs. Generally, mixed ionic (O(2-) ) and electronic conductors (MIECs) have been selected as the cathode material of H(+) -SOFCs. In an H(+) -SOFC system, however, MIEC cathodes limit the electrochemically active sites to the interface between the proton conducting electrolyte and the cathode. New approaches to the tailoring of cathode materials for H(+) -SOFCs should therefore be considered. TCOs can effectively extend the electrochemically active sites from the interface between the cathode and the electrolyte to the entire surface of the cathode. The electrochemical performance of NBSCF/BZCYYb/BZCYYb-NiO shows excellent long term stability for 500 h at 1023 K with high power density of 1.61 W cm(-2) .

  10. Copper sulfates as cathode materials for Li batteries

    NASA Astrophysics Data System (ADS)

    Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair

    As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO 4) 2- possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO 4·5H 2O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss.

  11. Discharge characteristics of lithium/molten nitrate thermal battery cells using silver salts as solid cathode materials

    NASA Astrophysics Data System (ADS)

    McManis, G. E.; Miles, M. H.; Fletcher, A. N.

    1985-12-01

    Thermal battery cells using molten nitrate electrolytes and liquid lithium anodes have been evaluated using several silver salts with low solubility in molten nitrates as solid cathode materials. These cathode materials do not readily diffuse into the anolyte and, thus, do not have parasitic reactions with the lithium anode. Furthermore, the solid cathode materials have voltammetric characteristics as favorable as many soluble silver salt cathodes. This paper presents the effects of temperature, current density, and cathode material on cell discharge characteristics.

  12. Alternate anode materials for cathodic protection of steel reinforced concrete

    SciTech Connect

    Russell, James H.; Bullard, Sophie J.; Covino, Bernard S., Jr.; Cramer, Stephen D.; Holcomb, Gordon R.; Cryer, Curtis B.

    2001-01-01

    Consumable and non-consumable anodes were evaluated in the laboratory for use in cathodic protection (CP) systems for steel reinforced concrete bridges in coastal environments and in areas where deicing salts are employed. The anode materials included Zn-hydrogel and thermal-sprayed Zn, Zn-15Al, Al-12Zn-0.2In, and cobalt-sprayed Ti. These anodes were evaluated for service in both galvanic (GCP) and impressed current (ICCP) cathodic protection systems. Impressed current CP anodes were electrochemically aged at a current density 15 times as great as that used by the Oregon Department of Transportation in typical coastal ICCP systems (2.2 mA/m2 based on anode area). Increasing moisture at the anode-concrete interface reduced the operating voltage of all the anodes. Bond strength between the anodes and concrete decreased with electrochemical aging. The Zn-15Al and Al-12Zn-0.2In anodes provided adequate protection in GCP but their life was too short in the accelerated ICCP tests. Zinc had an adequate life in ICCP tests but was inadequate as a galvanic anode. Zinc-hydrogel performed well in both tests when the hydrogel was kept moist. Titanium was an excellent anode for ICCP, but is not suitable for GCP.

  13. New Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Allan J. Jacobson

    2006-09-30

    Operation of SOFCs at intermediate temperatures (500-800 C) requires new combinations of electrolyte and electrode materials that will provide both rapid ion transport across the electrolyte and electrode-electrolyte interfaces and efficient electrocatalysis of the oxygen reduction and fuel oxidation reactions. This project concentrates on materials and issues associated with cathode performance that are known to become limiting factors as the operating temperature is reduced. The specific objectives of the proposed research are to develop cathode materials that meet the electrode performance targets of 1.0 W/cm{sup 2} at 0.7 V in combination with YSZ at 700 C and with GDC, LSGM or bismuth oxide based electrolytes at 600 C. The performance targets imply an area specific resistance of {approx}0.5 {Omega}cm{sup 2} for the total cell. The research strategy is to investigate both established classes of materials and new candidates as cathodes, to determine fundamental performance parameters such as bulk diffusion, surface reactivity and interfacial transfer, and to couple these parameters to performance in single cell tests. The initial choices for study were perovskite oxides based on substituted LaFeO{sub 3} (P1 compositions), where significant data in single cell tests exist at PNNL for example, for La{sub 0.8}Sr{sub 0.2}FeO{sub 3} cathodes on both YSZ and CSO/YSZ. The materials selection was then extended to La{sub 2}NiO{sub 4} compositions (K1 compositions), and then in a longer range task we evaluated the possibility of completely unexplored group of materials that are also perovskite related, the ABM{sub 2}O{sub 5+{delta}}. A key component of the research strategy was to evaluate for each cathode material composition, the key performance parameters, including ionic and electronic conductivity, surface exchange rates, stability with respect to the specific electrolyte choice, and thermal expansion coefficients. In the initial phase, we did this in parallel with

  14. Nanostructured material for advanced energy storage : magnesium battery cathode development.

    SciTech Connect

    Sigmund, Wolfgang M.; Woan, Karran V.; Bell, Nelson Simmons

    2010-11-01

    Magnesium batteries are alternatives to the use of lithium ion and nickel metal hydride secondary batteries due to magnesium's abundance, safety of operation, and lower toxicity of disposal. The divalency of the magnesium ion and its chemistry poses some difficulties for its general and industrial use. This work developed a continuous and fibrous nanoscale network of the cathode material through the use of electrospinning with the goal of enhancing performance and reactivity of the battery. The system was characterized and preliminary tests were performed on the constructed battery cells. We were successful in building and testing a series of electrochemical systems that demonstrated good cyclability maintaining 60-70% of discharge capacity after more than 50 charge-discharge cycles.

  15. Mercury vapor hollow cathode component studies. [emissive materials for ion thruster requirements

    NASA Technical Reports Server (NTRS)

    Zuccaro, D. E.

    1973-01-01

    An experimental study of starting and operating characteristics of conventional hollow cathodes and of hollow cathodes without alkaline earth emissive materials demonstrated that the emissive mix is essential to obtain the desired cathode operation. Loss of the emissive mix by evaporation and chemical reaction was measured. New insert designs consisting of emissive mix supported on nickel and of barium impregnated porous tungsten were studied. Cathodes with a modified orifice geometry operated in a low voltage, 'spot' mode over a broad range of discharge current. Thermal degradation tests on cathode heaters showed the flame sprayed SERT II type to be the most durable at high temperatures. Thermal shock was observed to be a significant factor in limiting cathode heater life. A cathode having a barium impregnated porous tungsten tip and a heater which is potted in sintered alumina was found to have favorable operating characteristics.

  16. Hydrogen Induced Stress Cracking of Materials Under Cathodic Protection

    NASA Astrophysics Data System (ADS)

    LaCoursiere, Marissa P.

    Hydrogen embrittlement of AISI 4340, InconelRTM 718, Alloy 686 and Alloy 59 was studied using slow strain rate tests of both smooth and notched cylindrical specimens. Two heat treatments of the AISI 4340 material were used as a standard for two levels of yield strength: 1479 MPa, and 1140 MPa. A subset of the 1140 MPa AISI 4340 material also underwent plasma nitriding. The InconelRTM 718 material was hardened following AMS 5663M to obtain a yield strength of 1091 MPa. The Alloy 686 material was obtained in the Grade 3 condition with a minimum yield strength of 1034 MPa. The Alloy 59 material was obtained with a cold worked condition similar to the Alloy 686 and with a minimum yield strength of 1034 MPa. Ninety-nine specimens were tested, including smooth cylindrical tensile test specimens and smooth and notched cylindrical slow strain rate tensile tests specimens. Testing included specimens that had been precharged with hydrogen in 3.5% NaCl at 50°C for 2 weeks (AISI 4340), 4 weeks (InconelRTM 718, Alloy 686, Alloy 59) and 16 weeks (InconelRTM 718, Alloy 686, Alloy 59) using a potentiostat to deliver a cathodic potential of -1100 mV vs. SCE. The strain rate over the gauge section for the smooth specimens and in the notch root for the notched specimens was 1 x 10-6 /s. It was found that the AISI 4340 was highly embrittled in simulated ocean water when compared to the nickel based superalloys. The higher strength AISI 4340 showed much more embrittlement, as expected. Testing of the AISI 4340 at both 20°C and 4°C showed that the temperature had no effect on the hydrogen embrittlement response. The InconelRTM 718 was highly embrittled when precharged, although it only showed low levels of embrittlement when unprecharged. Both the Alloy 686 and Alloy 59 showed minimal embrittlement in all conditions. Therefore, for the materials examined, the use of Alloy 686 and Alloy 59 for components in salt water environments when under a cathodic potential of -1100 mV vs. SCE is

  17. Lanthanides: new metallic cathode materials for organic photovoltaic cells.

    PubMed

    Nikiforov, Maxim P; Strzalka, Joseph; Jiang, Zhang; Darling, Seth B

    2013-08-21

    Organic photovoltaics (OPVs) are compliant with inexpensive, scalable, and environmentally benign manufacturing technologies. While substantial attention has been focused on optimization of active layer chemistry, morphology, and processing, far less research has been directed to understanding charge transport at the interfaces between the electrodes and the active layer. Electrical properties of these interfaces not only impact efficiency, but also play a central role in stability of organic solar cells. Low work function metals are the most widely used materials for the electron transport layer with Ca being the most common material. In bulk heterojunction OPV devices, low work function metals are believed to mirror the role they play in OLEDs, where such metals are used to control carrier selectivity, transport, extraction, and blocking, as well as interface band bending. Despite their advantages, low work function materials are generally prone to reactions with water, oxygen, nitrogen, and carbon dioxide from air leading to rapid device degradation. Here we discuss the search for a new metallic cathode interlayer material that increases device stability and still provides device efficiency similar to that achieved with a Ca interlayer.

  18. The influence of cathode material on electrochemical degradation of trichloroethylene in aqueous solution.

    PubMed

    Rajic, Ljiljana; Fallahpour, Noushin; Podlaha, Elizabeth; Alshawabkeh, Akram

    2016-03-01

    In this study, different cathode materials were evaluated for electrochemical degradation of aqueous phase trichloroethylene (TCE). A cathode followed by an anode electrode sequence was used to support reduction of TCE at the cathode via hydrodechlorination (HDC). The performance of iron (Fe), copper (Cu), nickel (Ni), aluminum (Al) and carbon (C) foam cathodes was evaluated. We tested commercially available foam materials, which provide large electrode surface area and important properties for field application of the technology. Ni foam cathode produced the highest TCE removal (68.4%) due to its high electrocatalytic activity for hydrogen generation and promotion of HDC. Different performances of the cathode materials originate from differences in the bond strength between atomic hydrogen and the material. With a higher electrocatalytic activity than Ni, Pd catalyst (used as cathode coating) increased TCE removal from 43.5% to 99.8% for Fe, from 56.2% to 79.6% for Cu, from 68.4% to 78.4% for Ni, from 42.0% to 63.6% for Al and from 64.9% to 86.2% for C cathode. The performance of the palladized Fe foam cathode was tested for degradation of TCE in the presence of nitrates, as another commonly found groundwater species. TCE removal decreased from 99% to 41.2% in presence of 100 mg L(-1) of nitrates due to the competition with TCE for HDC at the cathode. The results indicate that the cathode material affects TCE removal rate while the Pd catalyst significantly enhances cathode activity to degrade TCE via HDC.

  19. The influence of cathode material on electrochemical degradation of trichloroethylene in aqueous solution.

    PubMed

    Rajic, Ljiljana; Fallahpour, Noushin; Podlaha, Elizabeth; Alshawabkeh, Akram

    2016-03-01

    In this study, different cathode materials were evaluated for electrochemical degradation of aqueous phase trichloroethylene (TCE). A cathode followed by an anode electrode sequence was used to support reduction of TCE at the cathode via hydrodechlorination (HDC). The performance of iron (Fe), copper (Cu), nickel (Ni), aluminum (Al) and carbon (C) foam cathodes was evaluated. We tested commercially available foam materials, which provide large electrode surface area and important properties for field application of the technology. Ni foam cathode produced the highest TCE removal (68.4%) due to its high electrocatalytic activity for hydrogen generation and promotion of HDC. Different performances of the cathode materials originate from differences in the bond strength between atomic hydrogen and the material. With a higher electrocatalytic activity than Ni, Pd catalyst (used as cathode coating) increased TCE removal from 43.5% to 99.8% for Fe, from 56.2% to 79.6% for Cu, from 68.4% to 78.4% for Ni, from 42.0% to 63.6% for Al and from 64.9% to 86.2% for C cathode. The performance of the palladized Fe foam cathode was tested for degradation of TCE in the presence of nitrates, as another commonly found groundwater species. TCE removal decreased from 99% to 41.2% in presence of 100 mg L(-1) of nitrates due to the competition with TCE for HDC at the cathode. The results indicate that the cathode material affects TCE removal rate while the Pd catalyst significantly enhances cathode activity to degrade TCE via HDC. PMID:26761603

  20. Spectroscopic studies of cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Totir, Dana Alexa

    2000-10-01

    Structural changes that occur during electrochemical cycling of lithium-ion battery cathode materials have been investigated using in situ spectroscopic techniques. A new method was developed for the preparation of carbon and binder free cathodes utilizing powder materials of interest for commercial batteries. The extraordinary quality of the cyclic voltammetric curves recorded for this type of electrodes during the in situ measurements allows direct correlations to be made between the state of charge of the material and its structural and electronic characteristics. LiCoO2, LiMn2O4 and LiCo0.15Ni 0.85O2 electrodes were evaluated using cycling voltammetry and the mean diffusion coefficient for Li-ions in the lattice (DLi) was calculated for LiMn2O4. LiMn2O4 electrodes prepared by this technique have been studied in situ using Mn K-edge XAS. Data analysis for the species formed at different potentials indicated a contraction of the lattice associated with the increase in the oxidation state of manganese. In situ Raman spectra of particles of LiMn2O 4, and LiCoO2 embedded in Au and also of KS-44 graphite and carbon microfibers MCF28 embedded in thermally annealed Ni have been recorded as a function of the applied potential. Fe K-edge XAFS of pyrite electrodes in a Li/PEO(LiClO4)/FeS 2 cell and S K-edge XANES measurements of a FeS2 electrode in a non-aqueous electrolyte have been acquired as a function of the state of charge. The studies have clearly evidenced the formation of metallic Fe and Li2S as intermediates after 4 e- discharge and the formation of Li2FeS2 after 2 e- recharge. While Fe K-edge studies have indicated that there is no change in the Fe environment and oxidation state upon 4 e- recharge, the results obtained from S K-edge studies are inconclusive for this stage. Finally, in situ Co K-edge XAFS data were obtained for the first time during the electrochemical cycling of electrodeposited Co(OH) 2 films in alkaline solutions. The results support

  1. Organotrisulfide: A High Capacity Cathode Material for Rechargeable Lithium Batteries.

    PubMed

    Wu, Min; Cui, Yi; Bhargav, Amruth; Losovyj, Yaroslav; Siegel, Amanda; Agarwal, Mangilal; Ma, Ying; Fu, Yongzhu

    2016-08-16

    An organotrisulfide (RSSSR, R is an organic group) has three sulfur atoms which could be involved in multi-electron reduction reactions; therefore it is a promising electrode material for batteries. Herein, we use dimethyl trisulfide (DMTS) as a model compound to study its redox reactions in rechargeable lithium batteries. With the aid of XRD, XPS, and GC-MS analysis, we confirm DMTS could undergo almost a 4 e(-) reduction process in a complete discharge to 1.0 V. The discharge products are primarily LiSCH3 and Li2 S. The lithium cell with DMTS catholyte delivers an initial specific capacity of 720 mAh g(-1) DMTS and retains 82 % of the capacity over 50 cycles at C/10 rate. When the electrolyte/DMTS ratio is 3:1 mL g(-1) , the reversible specific energy for the cell including electrolyte can be 229 Wh kg(-1) . This study shows organotrisulfide is a promising high-capacity cathode material for high-energy rechargeable lithium batteries. PMID:27411083

  2. Organotrisulfide: A High Capacity Cathode Material for Rechargeable Lithium Batteries.

    PubMed

    Wu, Min; Cui, Yi; Bhargav, Amruth; Losovyj, Yaroslav; Siegel, Amanda; Agarwal, Mangilal; Ma, Ying; Fu, Yongzhu

    2016-08-16

    An organotrisulfide (RSSSR, R is an organic group) has three sulfur atoms which could be involved in multi-electron reduction reactions; therefore it is a promising electrode material for batteries. Herein, we use dimethyl trisulfide (DMTS) as a model compound to study its redox reactions in rechargeable lithium batteries. With the aid of XRD, XPS, and GC-MS analysis, we confirm DMTS could undergo almost a 4 e(-) reduction process in a complete discharge to 1.0 V. The discharge products are primarily LiSCH3 and Li2 S. The lithium cell with DMTS catholyte delivers an initial specific capacity of 720 mAh g(-1) DMTS and retains 82 % of the capacity over 50 cycles at C/10 rate. When the electrolyte/DMTS ratio is 3:1 mL g(-1) , the reversible specific energy for the cell including electrolyte can be 229 Wh kg(-1) . This study shows organotrisulfide is a promising high-capacity cathode material for high-energy rechargeable lithium batteries.

  3. Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

    NASA Technical Reports Server (NTRS)

    Rice, Catherine E.; Welker, Mark F.

    2008-01-01

    LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.

  4. Study Of Erosion Rates And Surface Effects of Different Hollow Cathode Materials During Vacuum Microarc Discharge

    SciTech Connect

    Atta Khedr, M.; Abdel Moneim, H.M.

    2005-03-17

    Studies of the properties of the emitted plasma from graphite, titanium, titanium Carbide, Stainless Steel, Cupper and Molybdenum Hollow Cathode materials during vacuum microarc were carried out. Using high voltage of 30 KV, short arc duration (0.5 - 4 {mu}s) and arc currents (100 - 450 A), each cathode material was subjected to 1000-3000 arc discharges under high vacuum (10-8 mbar) conditions. The angular distributions for the evaporants in each case were measured and show an exponential isotropic distribution in agreement with the theoretical predictions. The total erosion rates of evaporants and molten droplets were estimated and showed clearly their, dependence on the cathode material and on the hollow cathode geometry. The damages on the cathode surfaces and the inside of the hollow cathodes were investigated by the scanning electron microscope. Crater formation were formed spreading inside the hole of the hollow cathodes as well as on the rim surfaces and were found to differ according to both geometry and material of the hollow cathodes. The crater evacuation velocity and plasma pressure were determined. The damage on the anode tip showed erosion on the pen anode tip to the extent of drilling hole. The mechanism responsible for such phenomena is discussed.

  5. Particle size effect of Ni-rich cathode materials on lithium ion battery performance

    SciTech Connect

    Hwang, Ilkyu; Lee, Chul Wee; Kim, Jae Chang; Yoon, Songhun

    2012-01-15

    Graphical abstract: The preparation condition of Ni-rich cathode materials was investigated. When the retention time was short, a poor cathode performance was observed. For long retention time condition, cathode performance displayed a best result at pH 12. Highlights: Black-Right-Pointing-Pointer Ni-rich cathode materials (LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}) were prepared by co-precipitation method using separate addition of Al salt. Black-Right-Pointing-Pointer Particle size of Ni-rich cathode materials became larger with increase of retention time and solution pH. Black-Right-Pointing-Pointer Cathode performance was poor for low retention time. Black-Right-Pointing-Pointer Optimal pH for co-precipitation was 12. -- Abstract: Herein, Ni-rich cathode materials (LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}) in lithium ion batteries are prepared by a separate addition of Ni/Co salt and Al sol solution using a continuously stirred tank reactor. Retention time and solution pH were controlled in order to obtain high performance cathode material. Particle size increase was observed with a higher retention time of the reactants. Also, primary and secondary particles became smaller according to an increase of solution pH, which was probably due to a decrease of growth rate. From the cathode application, a high discharge capacity (175 mAh g{sup -1}), a high initial efficiency (90%) and a good cycleability were observed in the cathode material prepared under pH 12 condition, which was attributed to its well-developed layered property and the optimal particle size. However, rate capability was inversely proportional to the particle size, which was clarified by a decrease of charge-transfer resistance measured in the electrochemical impedance spectroscopy.

  6. High-Current Cold Cathode Employing Diamond and Related Materials

    SciTech Connect

    Hirshfield, Jay L.

    2014-10-22

    The essence of this project was for diamond films to be deposited on cold cathodes to improve their emission properties. Films with varying morphology, composition, and size of the crystals were deposited and the emission properties of the cathodes that utilize such films were studied. The prototype cathodes fabricated by the methods developed during Phase I were tested and evaluated in an actual high-power RF device during Phase II. These high-power tests used the novel active RF pulse compression system and the X-band magnicon test facility at US Naval Research Laboratory. In earlier tests, plasma switches were employed, while tests under this project utilized electron-beam switching. The intense electron beams required in the switches were supplied from cold cathodes embodying diamond films with varying morphology, including uncoated molybdenum cathodes in the preliminary tests. Tests with uncoated molybdenum cathodes produced compressed X-band RF pulses with a peak power of 91 MW, and a maximum power gain of 16.5:1. Tests were also carried out with switches employing diamond coated cathodes. The pulse compressor was based on use of switches employing electron beam triggering to effect mode conversion. In experimental tests, the compressor produced 165 MW in a ~ 20 ns pulse at ~18× power gain and ~ 140 MW at ~ 16× power gain in a 16 ns pulse with a ~ 7 ns flat-top. In these tests, molybdenum blade cathodes with thin diamond coatings demonstrated good reproducible emission uniformity with a 100 kV, 100 ns high voltage pulse. The new compressor does not have the limitations of earlier types of active pulse compressors and can operate at significantly higher electric fields without breakdown.

  7. A review of blended cathode materials for use in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Chikkannanavar, Satishkumar B.; Bernardi, Dawn M.; Liu, Lingyun

    2014-02-01

    Several commercial automotive battery suppliers have developed lithium ion cells which use cathodes that consist of a mixture of two different active materials. This approach is intended to take advantage of the unique properties of each material and optimize the performance of the battery with respect to the automotive operating requirements. Certain cathode materials have high coulombic capacity and good cycling characteristics, but are costly and exhibit poor thermal stability (e.g., LiNixCo1-x-yAlyO2). Alternately, other cathode materials exhibit good thermal stability, high voltage and high rate capability, but have low capacity (e.g., LiMn2O4). By blending two cathode materials the shortcomings of the parent materials could be minimized and the resultant blend can be tailored to have a higher energy or power density coupled with enhanced stability and lower cost. In this review, we survey the developing field of blended cathode materials from a new perspective. Targeting a range of cathode materials, we survey the advances in the field in the current review. Limitations, such as capacity decay due to metal dissolution are also discussed, as well as how the appropriate balance of characteristics of the blended materials can be optimized for hybrid- and electric-vehicle applications.

  8. Factors Affecting the Battery Performance of Anthraquinone-based Organic Cathode Materials

    SciTech Connect

    Xu, Wu; Read, Adam L.; Koech, Phillip K.; Hu, Dehong; Wang, Chong M.; Xiao, Jie; Padmaperuma, Asanga B.; Graff, Gordon L.; Liu, Jun; Zhang, Jiguang

    2012-02-01

    Two organic cathode materials based on poly(anthraquinonyl sulfide) structure with different substitution positions were synthesized and their electrochemical behavior and battery performances were investigated. The substitution positions on the anthraquinone structure, binders for electrode preparation and electrolyte formulations have been found to have significant effects on the battery performances of such organic cathode materials. The substitution position with less steric stress has higher capacity, longer cycle life and better high-rate capability. Polyvinylidene fluoride binder and ether-based electrolytes are favorable for the high capacity and long cycle life of the quinonyl organic cathodes.

  9. Hexagonal NiS nanobelts as advanced cathode materials for rechargeable Al-ion batteries.

    PubMed

    Yu, Zhijing; Kang, Zepeng; Hu, Zongqian; Lu, Jianhong; Zhou, Zhigang; Jiao, Shuqiang

    2016-08-16

    Hexagonal NiS nanobelts served as novel cathode materials for rechargeable Al-ion batteries based on an AlCl3/[EMIm]Cl ionic liquid electrolyte system. The nano-banded structure of the materials can facilitate the electrolyte immersion and enhance Al(3+) diffusion. The hexagonal NiS nanobelt based cathodes exhibit high storage capacity, good cyclability and low overpotential. PMID:27487940

  10. Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning.

    PubMed

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

    2015-12-01

    Cathode materials are difficult to separate from Al-foil substrates during the recycling of spent lithium-ion batteries (LIBs), because of the strong bonding force present. In this study, ultrasonic cleaning was used to separate and recycle these cathode materials. The mechanism of separation was ascribed to the dissolution of polyvinylidene fluoride (PVDF) and the cavitation caused by ultrasound. Based on this mechanism, the key parameters affecting the peel-off efficiency of cathode materials from Al foil was identified as solvent nature, temperature, ultrasonic power, and ultrasonic time. The peel-off efficiency of cathode materials achieved ∼ 99% under the optimized conditions of N-methyl-2-pyrrolidone (NMP) cleaning fluid, 70°C process temperature, 240 W ultrasonic power, and 90 min of ultrasonication. The cathode materials separated from Al foil displayed a low agglomeration degree, which is beneficial to the subsequent leaching process. Finally, a new, environmentally-sound process was proposed to efficiently recycle cathode materials and Al from spent LIBs, consisting of manual dismantling, ultrasonic cleaning, and picking.

  11. Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning.

    PubMed

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

    2015-12-01

    Cathode materials are difficult to separate from Al-foil substrates during the recycling of spent lithium-ion batteries (LIBs), because of the strong bonding force present. In this study, ultrasonic cleaning was used to separate and recycle these cathode materials. The mechanism of separation was ascribed to the dissolution of polyvinylidene fluoride (PVDF) and the cavitation caused by ultrasound. Based on this mechanism, the key parameters affecting the peel-off efficiency of cathode materials from Al foil was identified as solvent nature, temperature, ultrasonic power, and ultrasonic time. The peel-off efficiency of cathode materials achieved ∼ 99% under the optimized conditions of N-methyl-2-pyrrolidone (NMP) cleaning fluid, 70°C process temperature, 240 W ultrasonic power, and 90 min of ultrasonication. The cathode materials separated from Al foil displayed a low agglomeration degree, which is beneficial to the subsequent leaching process. Finally, a new, environmentally-sound process was proposed to efficiently recycle cathode materials and Al from spent LIBs, consisting of manual dismantling, ultrasonic cleaning, and picking. PMID:26323202

  12. Selenium and selenium-sulfur cathode materials for high-energy rechargeable magnesium batteries

    NASA Astrophysics Data System (ADS)

    Zhao-Karger, Zhirong; Lin, Xiu-Mei; Bonatto Minella, Christian; Wang, Di; Diemant, Thomas; Behm, R. Jürgen; Fichtner, Maximilian

    2016-08-01

    Magnesium (Mg) is an attractive metallic anode material for next-generation batteries owing to its inherent dendrite-free electrodeposition, high capacity and low cost. Here we report a new class of Mg batteries based on both elemental selenium (Se) and selenium-sulfur solid solution (SeS2) cathode materials. Elemental Se confined into a mesoporous carbon was used as a cathode material. Coupling the Se cathode with a metallic Mg anode in a non-nucleophilic electrolyte, the Se cathode delivered a high initial volumetric discharge capacity of 1689 mA h cm-3 and a reversible capacity of 480 mA h cm-3 was retained after 50 cycles at a high current density of 2 C. The mechanistic insights into the electrochemical conversion in Mg-Se batteries were investigated by microscopic and spectroscopic methods. The structural transformation of cyclic Se8 into chainlike Sen upon battery cycling was revealed by ex-situ Raman spectroscopy. In addition, the promising battery performance with a SeS2 cathode envisages the perspective of a series of SeSn cathode materials combining the benefits of both selenium and sulfur for high energy Mg batteries.

  13. Role of surface coating on cathode materials for lithium-ion batteries.

    SciTech Connect

    Chen, Z.; Qin, Y.; Amine, K.; Sun, Y.-K.

    2010-01-01

    Surface coating of cathode materials has been widely investigated to enhance the life and rate capability of lithium-ion batteries. The surface coating discussed here was divided into three different configurations which are rough coating, core shell structure coating and ultra thin film coating. The mechanism of surface coating in achieving improved cathode performance and strategies to carry out this surface modification is discussed. An outlook on atomic layer deposition for lithium ion battery is also presented.

  14. Final Report on Materials Characterization for the Wetted Cathodes for Low-Temperature Aluminum Smelting Program

    SciTech Connect

    Windisch, Charles F.

    2002-10-30

    This report is a summary of materials characterization results on twenty cathode samples that were used in a novel aluminum reduction cell at the Northwest Aluminum Technologies laboratory. Most of these cathodes were based on the TiB2 composition and showed very little corrosion as a result of testing. Most of the samples also showed good wetting by Al metal that formed during cell operation.

  15. Carbon incorporation effects and reaction mechanism of FeOCl cathode materials for chloride ion batteries

    PubMed Central

    Zhao, Xiangyu; Li, Qiang; Yu, Tingting; Yang, Meng; Fink, Karin; Shen, Xiaodong

    2016-01-01

    Metal oxychlorides are proved to be new cathode materials for chloride ion batteries. However, this kind of cathode materials is still in a very early stage of research and development. The obtained reversible capacity is low and the electrochemical reaction mechanism concerning chloride ion transfer is not clear. Herein, we report FeOCl/carbon composites prepared by mechanical milling of the as-prepared FeOCl with carbon nanotube, carbon black or graphene nanoplatelets as cathode materials for chloride ion batteries. The electrochemical performance of the FeOCl electrode is evidently improved by the incorporation of graphene into the cathode. FeOCl/graphene cathode shows a high reversible capacity of 184 mAh g−1 based on the phase transformation between FeOCl and FeO. Two stages of this phase transformation are observed for the FeOCl cathode. New insight into the reaction mechanism of chloride ion dissociation of FeOCl is investigated by DFT + U + D2 calculations. PMID:26777572

  16. On the dispersion of lithium-sulfur battery cathode materials effected by electrostatic and stereo-chemical factors of binders

    NASA Astrophysics Data System (ADS)

    Hong, Xiaoheng; Jin, Jun; Wen, Zhaoyin; Zhang, Sanpei; Wang, Qingsong; Shen, Chen; Rui, Kun

    2016-08-01

    Sodium carboxymethyl cellulose-styrene butadiene rubber (CMC-SBR), sodium alginate (SA) and LA132 are utilized as the polymer binders for the cathodes of Li-S batteries to study their dispersion mechanism on the cathode materials and the consequent influence on the performance of Li-S batteries. Zeta potential tests, differential scanning calorimetry analysis and calculations of the rotational barriers of the links of the polymer chains by General Atomic and Molecular Electronic Structure System (GAMESS) reveal that higher charge densities and better chain flexibility of the binders promise the dispersion of the downsized cathode materials. LA132 is found to have optimal characteristic for dispersing and stabilizing the cathode materials in aqueous environment. The cycling performance and SEM images of the cathodes demonstrate that cathodes with higher dispersion degree achieve higher discharge capacities. The electrochemical impedance spectroscopy (EIS) results further support that better dispersed cathodes have lower impedance resulting from their well established conducting frameworks.

  17. Recent Advances and Prospects of Cathode Materials for Sodium-Ion Batteries.

    PubMed

    Xiang, Xingde; Zhang, Kai; Chen, Jun

    2015-09-23

    Sodium-ion batteries (SIBs) receive significant attention for electrochemical energy storage and conversion owing to their wide availability and the low cost of Na resources. However, SIBs face challenges of low specific energy, short cycling life, and insufficient specific power, owing to the heavy mass and large radius of Na(+) ions. As an important component of SIBs, cathode materials have a significant effect on the SIB electrochemical performance. The most recent advances and prospects of inorganic and organic cathode materials are summarized here. Among current cathode materials, layered transition-metal oxides achieve high specific energies around 600 mW h g(-1) owing to their high specific capacities of 180-220 mA h g(-1) and their moderate operating potentials of 2.7-3.2 V (vs Na(+) /Na). Porous Na3 V2 (PO4 )3 /C nanomaterials exhibit excellent cycling performance with almost 100% retention over 1000 cycles owing to their robust structural framework. Recent emerging cathode materials, such as amorphous NaFePO4 and pteridine derivatives show interesting electrochemical properties and attractive prospects for application in SIBs. Future work should focus on strategies to enhance the overall performance of cathode materials in terms of specific energy, cycling life, and rate capability with cationic doping, anionic substitution, morphology fabrication, and electrolyte matching.

  18. Carbyne polysulfide as a novel cathode material for rechargeable magnesium batteries.

    PubMed

    NuLi, Yanna; Chen, Qiang; Wang, Weikun; Wang, Ying; Yang, Jun; Wang, Jiulin

    2014-01-01

    We report the formation of carbyne polysulfide by coheating carbon containing carbyne moieties and elemental sulfur. The product is proved to have a sp2 hybrid carbon skeleton with polysulfide attached on it. The electrochemical performance of carbyne polysulfide as a novel cathode material for rechargeable magnesium batteries is firstly investigated. The material exhibits a high discharge capacity of 327.7 mAh g(-1) at 3.9 mA g(-1). These studies show that carbyne polysulfide is a promising candidate as cathode material for rechargeable Mg batteries if the capacity retention can be significantly improved.

  19. Studies on niobium triselenide cathode material for lithium rechargeable cells

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Ni, C. L.; Distefano, S.; Somoano, R. B.; Bankston, C. P.

    1988-01-01

    NbSe3 exhibits superior characteristics such as high capacity, high volumetric and gravimetric energy densities, and high discharge rate capability, as compared to other intercalating cathodes. This paper reports the preparation, characterization, and performance of NbSe3. Several electrochemical techniques, such as cyclic voltammetry, constant-current/constant-potential discharges, dc potentiodynamic scans, ac impedance, and ac voltammetry, have been used to give insight to the mechanisms of intercalation of three lithiums with NbSe3 and also into the rate determining process in the reduction of NbSe3.

  20. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  1. Chemical compatibility study of melilite-type gallate solid electrolyte with different cathode materials

    NASA Astrophysics Data System (ADS)

    Mancini, Alessandro; Felice, Valeria; Natali Sora, Isabella; Malavasi, Lorenzo; Tealdi, Cristina

    2014-05-01

    Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La1.50Sr0.50Ga3O7.25 has been extensively investigated by X-ray powder diffraction in a wide temperature range (up to 1573 K). Perovskite-type La0.8Sr0.2MnO3-d and La0.8Sr0.2Fe0.8Cu0.2O3-d and K2NiF4-type La2NiO4+d were selected as cathode materials. The results of this study allow identifying the most suitable electrode material to be used in combination with the melilite-type gallate electrolyte and set the basis for future work on this novel system.

  2. Cathode material for lithium ion accumulators prepared by screen printing for Smart Textile applications

    NASA Astrophysics Data System (ADS)

    Syrový, T.; Kazda, T.; Syrová, L.; Vondrák, J.; Kubáč, L.; Sedlaříková, M.

    2016-03-01

    The presented study is focused on the development of LiFePO4 based cathode for thin and flexible screen printed secondary lithium based accumulators. An ink formulation was developed for the screen printing technique, which enabled mass production of accumulator's cathode for Smart Label and Smart Textile applications. The screen printed cathode was compared with an electrode prepared by the bar coating technique using an ink formulation based on the standard approach of ink composition. Obtained LiFePO4 cathode layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and galvanostatic charge/discharge measurements at different loads. The discharge capacity, capacity retention and stability at a high C rate of the LiFePO4 cathode were improved when Super P and PVDF were replaced by conductive polymers PEDOT:PSS. The achieved capacity during cycling at various C rates was approximately the same at the beginning and at the end, and it was about 151 mAh/g for cycling under 1C. The obtained results of this novelty electrode layer exceed the parameters of several electrode layers based on LiFePO4 published in literature in terms of capacity, cycling stability and overcomes them in terms of simplicity/industrial process ability of cathode layer fabrication and electrode material preparation.

  3. Electrochemical properties of cathodic materials synthesized by low-temperature techniques

    NASA Astrophysics Data System (ADS)

    Pereira-Ramos, Jean-Pierre

    After having introduced the definition of 'low temperature techniques', the electrochemical properties of various cathodic materials (oxides) for secondary lithium batteries are reported. The influence of the way of synthesis upon their electrochemical behaviour is examined and illustrated through several examples. A presentation of electrochemical results discussed in relation with the specific chemical, physical and structural properties emphasizes the significant advances afforded by these techniques (sol-gel processes, precipitation, ion-exchange redox reactions, etc.) in obtaining new high-performance cathodic materials for secondary lithium batteries. The most interesting results are obtained for the vanadium and manganese systems.

  4. Hollow nanoparticle cathode materials for sodium electrochemical cells and batteries

    DOEpatents

    Shevchenko, Elena; Rajh, Tijana; Johnson, Christopher S.; Koo, Bonil

    2016-07-12

    A cathode comprises, in its discharged state, a layer of hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles disposed between two layers of carbon nanotubes, and preferably including a metallic current collector in contact with one of the layers of carbon nanotubes. Individual particles of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles comprise a crystalline shell of .gamma.-Fe.sub.2O.sub.3 including cation vacancies within the crystal structure of the shell (i.e., iron vacancies of anywhere between 3% to 90%, and preferably 44 to 77% of available octahedral iron sites). Sodium ions are intercalated within at least some of the cation vacancies within the crystalline shell of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles.

  5. Li-rich layer-structured cathode materials for high energy Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Liu; Lee, Kim Seng; Lu, Li

    2014-08-01

    Li-rich layer-structured xLi2MnO3 ṡ (1 - x)LiMO2 (M = Mn, Ni, Co, etc.) materials have attracted much attention due to their extraordinarily high reversible capacity as the cathode material in Li-ion batteries. To better understand the nature of this type of materials, this paper reviews history of development of the Li-rich cathode materials, and provides in-depth study on complicated crystal structures and reaction mechanisms during electrochemical charge/discharge cycling. Despite the fabulous capability at low rate, several drawbacks still gap this type of high-capacity cathode materials from practical applications, for instance the large irreversible capacity loss at first cycle, poor rate capability, severe voltage decay and capacity fade during electrochemical charge/discharge cycling. This review will also address mechanisms for these inferior properties and propose various possible solutions to solve above issues for future utilization of these cathode materials in commercial Li-ion batteries.

  6. Synthesis, Characterization and Testing of Novel Anode and Cathode Materials for Li-Ion Batteries

    SciTech Connect

    White, Ralph E.; Popov, Branko N.

    2002-10-31

    During this program we have synthesized and characterized several novel cathode and anode materials for application in Li-ion batteries. Novel synthesis routes like chemical doping, electroless deposition and sol-gel method have been used and techniques like impedance, cyclic voltammetry and charge-discharge cycling have been used to characterize these materials. Mathematical models have also been developed to fit the experimental result, thus helping in understanding the mechanisms of these materials.

  7. Aerospace applications of sodium batteries using novel cathode materials

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Di Stefano, S.; Bankston, C. P.

    1989-01-01

    Preliminary fundamental investigations aimed at evaluating sodium metal chloride systems for future aerospace applications are described. Since the sodium metal chloride systems are relatively new, the approach has been to characterize their fundamental properties in order to understand their limitations. To this end, a series of fundamental electrochemical investigations have been carried out, the results of which are reported here. The metal chloride cathodes show high exchange current densities which corroborate their good reversibility in a battery application. The reduction mechanisms appear to be complex and involve multielectron transfer steps and intermediates. Such intermediates in the reaction mechanism have already been identified in the case of FeCl2. Similar mechanisms may be operative in the case of NiCl2. CuCl2, however, exhibits a second relaxation loop in the impedance plot at low frequencies and also a sloping discharge curve, unlike FeCl2 and NiCl2, which may indicate the existence of monovalent copper in the reduction mechanism.

  8. Catalyzed electrochemical gasification of carbonaceous materials at anode and electrowinning of metals at cathode

    SciTech Connect

    Vaughan, R.J.

    1983-09-20

    The electrochemical gasification reaction of carbonaceous materials by anodic oxidation in an aqueous acidic electrolyte to produce oxides of carbon at the anode and metallic elements at the cathode of an electrolysis cell is catalyzed by the use of an iron catalyst.

  9. Anode and cathode materials characterization for a microbial fuel cell in half cell configuration.

    PubMed

    Pant, Deepak; Van Bogaert, Gilbert; Porto-Carrero, Christof; Diels, Ludo; Vanbroekhoven, Karolien

    2011-01-01

    Microbial fuel cells (MFCs) are novel bioelectrochemical devices for spontaneous conversion of biomass into electricity through the metabolic activity of the bacteria. Microbial production of electricity may become an important source of bioenergy in future because MFCs offer the possibility of extracting electric current from a wide range of soluble or dissolved complex organic wastes and renewable biomass. However, the materials used in these devices are still not economic and researchers use different materials as cathode and anode in MFCs. This results in variable performance which is difficult to compare. We tested several commercially available materials for their suitability as anode in an acetate fed MFC. Besides, a novel non-platinized activated carbon (AC) based, gas porous air cathode was also tested. Both the anode and cathode were tested in a half cell configuration. Carbon cloth, graphite cloth and dynamically stable anode (DSA) served as ideal anode material with carbon cloth and graphite mesh reaching the open circuit voltage (OCV) of acetate oxidation (-500 mV vs. Ag/AgCl). The effect of increasing concentration of acetate on anode OCV was also investigated and results showed that on increasing the acetate concentration from 10 mM to 40 mM has no adverse impact on the anodic activity towards electrochemical oxidation of acetate. The AC cathode showed stable current (-1.2 mA/cm2) over a period of 100 days. PMID:21977673

  10. The dissolution mechanism of cathodic active materials of spent Zn-Mn batteries in HCl.

    PubMed

    Li, Yunqing; Xi, Guoxi

    2005-12-01

    The cathodic active materials of spent Zn-Mn batteries are complicated. The majority materials that they contain are Mn(OH)(2), Mn(2)O(4), lambda-Mn(2)O(2), ZnMn(2)O(4), Zn(NH(3))(2)Cl(2), [Zn(OH)(2)](4).ZnCl(2), etc. Dissolving these kinds of materials is important to the environmental pollution control and materials recycle. In present paper we investigated the dissolution mechanism of the cathodic active materials in HCl by testing the factors that can influence the dissolution procedure, including temperature, time, and the concentration of HCl and H(2)O(2). Our results showed that both neutralization and oxidation-reduction reactions occurred in the dissolution process, and that H(2)O(2) had a great effect on the dissolution efficiency.

  11. Different materials as a cathode modification layer on the impact of organic solar cells

    NASA Astrophysics Data System (ADS)

    Zhong, Jian; Huang, Qiuyan; Yu, Junsheng; Jiang, Yadong

    2010-10-01

    Organic thin film solar cells based on conjugated polymer or small molecules have showed an interesting approach to energy conversion since Tang reported a single donor-accepter hetero-junction solar cell. The power conversion efficiency of organic solar cells has increased steadily over last decade. Small-molecular weight organic double heterojunction donor-acceptor layer organic solar cells (OSC) with a structure of indium-tin-oxide (ITO)/CuPc(200Å)/C60(400Å)/x/Ag(1000Å), using CuPc(copper Phthalocyanine)as donor layer, and Alq3(8-Hydroxyquinoline aluminum salt), BCP(Bromocresol purple sodium salt) and Bphen(4'7-diphyenyl-1,10-phenanthroline) as cathode modification layer, respectively were fabricated. The performance of OSC was studied as a function of the different materials as an cathode modification layer to optimize the structure. The current-voltage characteristic of the solar cell under AM1.5 solar illumination at an intensity of 100 mw/cm2 showed that the power conversion efficiency (PCE) was dependent of the different materials of the cathode modification layer. the efficiency along with the different materials as an cathode modification layer will diminish under that standard solar illumination(AM1.5)was obtained. Using a double heterostructure of ITO/CuPc(200Å)/C60(400Å)/Alq3(60Å)/Ag(1000Å) with high-vacuum evaporation technology, the efficiency was 0.587%.the efficiency was 0.967% when the material of the cathode modification layer was BCP, with the structure of ITO/CuPc(200Å)/C60(400Å)/BCP(35Å)/Ag(1000Å), and the efficiency was 0.742% when the material of the cathode modification layer was Bphen, with the structure of ITO/CuPc(200Å)/C60(400Å)/ Bphen(50Å)/Ag(1000Å).Using different materials as a cathode modification layer, it can be seen that the material which matches the energy level could even eventually be able to improve the energy conversion efficiency more.

  12. Materials characterization of impregnated W and W-Ir cathodes after oxygen poisoning

    NASA Astrophysics Data System (ADS)

    Polk, James E.; Capece, Angela M.

    2015-05-01

    Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten-iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W-Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W-Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W-Ir. However, the W-Ir emitter exhibited less erosion and redeposition at the upstream end than the pure W emitter.

  13. Mitigating voltage fade in cathode materials by improving the atomic level uniformity of elemental distribution.

    PubMed

    Zheng, Jianming; Gu, Meng; Genc, Arda; Xiao, Jie; Xu, Pinghong; Chen, Xilin; Zhu, Zihua; Zhao, Wenbo; Pullan, Lee; Wang, Chongmin; Zhang, Ji-Guang

    2014-05-14

    Lithium- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being well understood. Here we report for the first time the mitigation of voltage and energy fade of LMR cathodes by improving the atomic level spatial uniformity of the chemical species. The results reveal that LMR cathodes (Li[Li0.2Ni0.2M0.6]O2) prepared by coprecipitation and sol-gel methods, which are dominated by a LiMO2 type R3̅m structure, show significant nonuniform Ni distribution at particle surfaces. In contrast, the LMR cathode prepared by a hydrothermal assisted method is dominated by a Li2MO3 type C2/m structure with minimal Ni-rich surfaces. The samples with uniform atomic level spatial distribution demonstrate much better capacity retention and much smaller voltage fade as compared to those with significant nonuniform Ni distribution. The fundamental findings on the direct correlation between the atomic level spatial distribution of the chemical species and the functional stability of the materials may also guide the design of other energy storage materials with enhanced stabilities.

  14. An investigation of anode and cathode materials in photomicrobial fuel cells.

    PubMed

    Schneider, Kenneth; Thorne, Rebecca J; Cameron, Petra J

    2016-02-28

    Photomicrobial fuel cells (p-MFCs) are devices that use photosynthetic organisms (such as cyanobacteria or algae) to turn light energy into electrical energy. In a p-MFC, the anode accepts electrons from microorganisms that are either growing directly on the anode surface (biofilm) or are free floating in solution (planktonic). The nature of both the anode and cathode material is critical for device efficiency. An ideal anode is biocompatible and facilitates direct electron transfer from the microorganisms, with no need for an electron mediator. For a p-MFC, there is the additional requirement that the anode should not prevent light from perfusing through the photosynthetic cells. The cathode should facilitate the rapid reaction of protons and oxygen to form water so as not to rate limit the device. In this paper, we first review the range of anode and cathode materials currently used in p-MFCs. We then present our own data comparing cathode materials in a p-MFC and our first results using porous ceramic anodes in a mediator-free p-MFC. PMID:26755764

  15. Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution

    SciTech Connect

    Zheng, Jianming; Gu, Meng; Genc, Arda; Xiao, Jie; Xu, Pinghong; Chen, Xilin; Zhu, Zihua; Zhao, Wenbo; Pullan, Lee; Wang, Chong M.; Zhang, Jiguang

    2014-04-07

    Li-rich and Mn-rich (LMR) layered structured materials are very promising cathodes for high-energy lithium-ion batteries. However, their fundamental structure and voltage fading mechanisms are far from being well understood. Here we report the first evidence on the reduced voltage and energy fade of LMR cathode by improving the atomic level spatial distribution of the chemical species. LMR cathode (Li[Li0.2Ni0.2M0.6]O2) prepared by co-precipitation and sol-gel methods are dominated by R-3m phase and show significant Ni-segregation at the surface of the particles. They exhibit large voltage-fade and fast capacity degradation. In contrast, LMR cathode prepared by hydrothermal assisted method is dominated by C2/m phase and minimal Ni-segregation. It also demonstrates much smaller voltage-fade and excellent capacity retention. The fundamental correlation between the atomic level spatial distribution of the chemical species and the functional stability of the materials found in this work also guide the design of other functional materials with enhanced stabilities.

  16. An investigation of anode and cathode materials in photomicrobial fuel cells.

    PubMed

    Schneider, Kenneth; Thorne, Rebecca J; Cameron, Petra J

    2016-02-28

    Photomicrobial fuel cells (p-MFCs) are devices that use photosynthetic organisms (such as cyanobacteria or algae) to turn light energy into electrical energy. In a p-MFC, the anode accepts electrons from microorganisms that are either growing directly on the anode surface (biofilm) or are free floating in solution (planktonic). The nature of both the anode and cathode material is critical for device efficiency. An ideal anode is biocompatible and facilitates direct electron transfer from the microorganisms, with no need for an electron mediator. For a p-MFC, there is the additional requirement that the anode should not prevent light from perfusing through the photosynthetic cells. The cathode should facilitate the rapid reaction of protons and oxygen to form water so as not to rate limit the device. In this paper, we first review the range of anode and cathode materials currently used in p-MFCs. We then present our own data comparing cathode materials in a p-MFC and our first results using porous ceramic anodes in a mediator-free p-MFC.

  17. Chemically synthesized boron carbon oxynitride as a new cold cathode material

    NASA Astrophysics Data System (ADS)

    Banerjee, Diptonil; Maity, Supratim; Chattopadhyay, K. K.

    2015-11-01

    Synthesis of boron carbon oxynitride (BCNO) nanosheets at different temperature from amorphous to crystalline regime has been reported. The synthesis was done by a simple molten salt process using sodium borohydride and urea as precursors. Transmission electron microscopic study confirms the formation of sheet-like structure of the as-synthesized material. The performances of the as-synthesized BCNO nanosheets as cold cathode materials have been studied for the first time in the high vacuum electron field emission set up. It has been seen that the material gives considerable field emission current with turn on field as low as 2.95 V/μm with good stability and thus a new cold cathode material can be postulated.

  18. Electron microscopy characterization of Li-based cathode materials for battery applications

    NASA Astrophysics Data System (ADS)

    Phillips, Patrick; Klie, Robert

    2014-03-01

    The role of aberration-corrected scanning transmission electron microscopy (STEM) in materials characterization is examined with respect to Li-based cathode materials for battery applications. STEM-based methods are quickly becoming the most promising characterization tools for these materials, owed largely to the wide-range of techniques available on advanced STEM instruments, including the direct imaging of both heavy and light elements, and both energy-dispersive X-ray (EDX) and electron energy loss (EEL) spectroscopies. The current talk with focus on structural and chemical characterization of a Li-based cathode material, both in a pristine and irradiated state. Focus will remain on the nucleation of structural transitions, while also characterizing relevant parameters such as the manganese valence and oxygen presence. Various imaging modes, including high/low angle annular dark field (H/LAADF) and annular bright field (ABF), in conjunction with EELS, will be used extensively for this analysis.

  19. Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

    SciTech Connect

    Zheng, Jianming; Xu, Pinghong; Gu, Meng; Xiao, Jie; Browning, Nigel D.; Yan, Pengfei; Wang, Chong M.; Zhang, Jiguang

    2015-02-24

    Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defect spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.

  20. Hydrothermal vanadium manganese oxides: Anode and cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Simões, Mário; Surace, Yuri; Yoon, Songhak; Battaglia, Corsin; Pokrant, Simone; Weidenkaff, Anke

    2015-09-01

    Vanadium manganese oxides with Mn content up to 33 at% were synthesized by a low temperature hydrothermal route allowing for the preparation of both anodic and cathodic materials for Li-ion batteries. Low amounts of manganese (below 13 at%) lead to the formation of elongated particles of layered hydrated vanadium oxides with manganese and water intercalated between the V2O5 slabs, while for higher Mn content of 33 at%, monoclinic MnV2O6 is formed. Former materials are suitable for high energy cathodes while the latter one is an anodic compound. The material containing 10 at% Mn has the composition Mn0.2V2O5·0.9H2O and shows the best cathodic activity with 20% capacity improvement over V2O5·0.5H2O. Lithiated MnV2O6 with Li5MnV2O6 composition prepared electrochemically was evaluated for the first time as anode in a full-cell against Mn0.2V2O5·0.9H2O cathode. An initial capacity ca. 300 A h kg-1 was measured with this battery corresponding to more than 500 Wh kg-1. These results confirm the prospect of using Li5MnV2O6 anodes in lithium-ion batteries as well as high-capacity layered hydrated vanadium oxides cathodes such as V2O5·0.5H2O and Mn0.2V2O5·0.9H2O.

  1. Synthesis and investigation of novel cathode materials for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Sawicki, Monica

    Environmental pollution and eventual depletion of fossil fuels and lithium has increased the need for research towards alternative electrical energy storage systems. In this context, research in sodium ion batteries (NIBs) has become more prevalent since the price in lithium has increased due to its demand and reserve location. Sodium is an abundant resource that is low cost, and safe; plus its chemical properties are similar to that of Li which makes the transition into using Na chemistry for ion battery systems feasible. In this study, we report the effects of processing conditions on the electrochemical properties of Na-ion batteries made of the NaCrO2 cathode. NaCrO2 is synthesized via solid state reactions. The as-synthesized powder is then subjected to high-energy ball milling under different conditions which reduces particle size drastically and causes significant degradation of the specific capacity for NaCrO2. X-ray diffraction reveals that lattice distortion has taken place during high-energy ball milling and in turn affects the electrochemical performance of the cathode material. This study shows that a balance between reducing particle size and maintaining the layered structure is essential to obtain high specific capacity for the NaCrO2 cathode. In light of the requirements for grid scale energy storage: ultra-long cycle life (> 20,000 cycles and calendar life of 15 to 20 years), high round trip efficiency (> 90%), low cost, sufficient power capability, and safety; the need for a suitable cathode materials with excellent capacity retention such as Na2MnFe(CN)6 and K2MnFe(CN)6 will be investigated. Prussian blue (A[FeIIIFeII (CN)6]•xH2O, A=Na+ or K+ ) and its analogues have been investigated as an alkali ion host for use as a cathode material. Their structure (FCC) provides large ionic channels along the direction enabling facile insertion and extraction of alkali ions. This material is also capable of more than one Na ion insertion per unit formula

  2. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  3. Theoretical investigation of Chevrel phase materials for cathodes accommodating Ca2+ ions

    NASA Astrophysics Data System (ADS)

    Smeu, Manuel; Hossain, Md Sazzad; Wang, Zi; Timoshevskii, Vladimir; Bevan, Kirk H.; Zaghib, Karim

    2016-02-01

    The Chevrel phase compounds Mo6X8 (X = S, Se, Te) are theoretically studied by ab initio methods as potential candidates for battery cathode materials. The voltage profiles are calculated for the cases of various alkaline earth metals (Mg, Ca, Sr, Ba) serving as guest intercalation ions. The Ca ions are shown to offer the practically significant voltage of ∼1.0-1.25 V, with S substitution giving the highest voltage over Se and Te. We further demonstrate that doubling the capacity of such a battery would also be possible by incorporating a second Ca ion near the Mo6X8 cluster. The electronic properties of this material are investigated, revealing that the entire Mo6 cluster behaves as a redox center. Finally, the ion diffusion barriers are calculated, showing comparable values to existing battery materials. This work demonstrates that the Chevrel phase may be useful as a cathode material for intercalating divalent ions, and also offers insights into possible tuning of cathode properties by judicious selection of the constituents.

  4. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  5. Bare-tether cathodic contact through thermionic emission by low-work-function materials

    SciTech Connect

    Chen Xin; Sanmartin, J. R.

    2012-07-15

    A new material, C12A7:e{sup -} electride, which might present a work function as low as 0.6 eV and moderately high temperature stability, was recently proposed as coating for floating bare tethers. Arising from heating under space operation, current is emitted by thermionic emission along a thus coated cathodic segment. A preliminary study on the space-charge-limited (SCL) double layer in front of the cathodic segment is presented using Langmuir's SCL electron current between cylindrical electrodes and orbital-motion-limited ion-collection sheath. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects and the transition from SCL to full Richardson-Dushman emission included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission leads to a short cathodic section and may eliminate the need for an active cathodic device and its corresponding gas feed requirements and power subsystem, which results in a truly 'propellant-less' tether system for such basic applications as de-orbiting low earth orbit satellites.

  6. Electron-deficient anthraquinone derivatives as cathodic material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Takeda, Takashi; Taniki, Ryosuke; Masuda, Asuna; Honma, Itaru; Akutagawa, Tomoyuki

    2016-10-01

    We studied the electronic and structural properties of electron-deficient anthraquinone (AQ) derivatives, Me4N4AQ and TCNAQ, and investigated their charge-discharge properties in lithium ion batteries along with those of AQ. Cyclic voltammogram, X-ray structure analysis and theoretical calculations revealed that these three acceptors have different features, such as different electron-accepting properties with different reduction processes and lithium coordination abilities, and different packing arrangements with different intermolecular interactions. These differences greatly affect the charge-discharge properties of lithium ion batteries that use these compounds as cathode materials. Among these compounds, Me4N4AQ showed a high charge/discharge voltage (2.9-2.5 V) with high cyclability (>65% of the theoretical capacity after 30 cycles; no decrease after 15 cycles). These results provide insight into more in-depth design principles for lithium ion batteries using AQ derivatives as cathodic materials.

  7. Graphene Modified LiFePO4 Cathode Materials for High Power Lithium ion Batteries

    SciTech Connect

    Zhou, X.; Wang, F.; Zhu, Y.; Liu, Z.

    2011-01-24

    Graphene-modified LiFePO{sub 4} composite has been developed as a Li-ion battery cathode material with excellent high-rate capability and cycling stability. The composite was prepared with LiFePO{sub 4} nanoparticles and graphene oxide nanosheets by spray-drying and annealing processes. The LiFePO{sub 4} primary nanoparticles embedded in micro-sized spherical secondary particles were wrapped homogeneously and loosely with a graphene 3D network. Such a special nanostructure facilitated electron migration throughout the secondary particles, while the presence of abundant voids between the LiFePO{sub 4} nanoparticles and graphene sheets was beneficial for Li{sup +} diffusion. The composite cathode material could deliver a capacity of 70 mAh g{sup -1} at 60C discharge rate and showed a capacity decay rate of <15% when cycled under 10C charging and 20C discharging for 1000 times.

  8. Introduction of two lithiooxycarbonyl groups enhances cyclability of lithium batteries with organic cathode materials

    NASA Astrophysics Data System (ADS)

    Shimizu, Akihiro; Kuramoto, Hiroki; Tsujii, Yutaka; Nokami, Toshiki; Inatomi, Yuu; Hojo, Nobuhiko; Suzuki, Hirotetsu; Yoshida, Jun-ichi

    2014-08-01

    To increase the cyclability of lithium batteries using organic cathode materials of low molecular weights, two lithiooxycarbonyl (-CO2Li) groups was introduced to p- and o-quinones. The introduction of two -CO2Li groups does not strongly affect the redox potentials of quinones. Lithium batteries using p- and o-quinones with two -CO2Li groups as cathode materials exhibit excellent cyclability compared to their parent quinones. In particular, pyrene-4,5,9,10-tetraone having two lithiooxycarbonyl groups (LCPYT) exhibited high energy density, high cyclability, and fast charge ability. These results indicate that introduction of two lithiooxycarbonyl groups to quinones serves as a simple and effective way to decrease the solubility of various quinones in electrolyte solutions without significant decrease in the voltage.

  9. Chemical compatibility study of melilite-type gallate solid electrolyte with different cathode materials

    SciTech Connect

    Mancini, Alessandro; Felice, Valeria; Natali Sora, Isabella; Malavasi, Lorenzo; Tealdi, Cristina

    2014-05-01

    Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by X-ray powder diffraction in a wide temperature range (up to 1573 K). Perovskite-type La{sub 0.8}Sr{sub 0.2}MnO{sub 3−d} and La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and K{sub 2}NiF{sub 4}-type La{sub 2}NiO{sub 4+d} were selected as cathode materials. The results of this study allow identifying the most suitable electrode material to be used in combination with the melilite-type gallate electrolyte and set the basis for future work on this novel system. - Graphical abstract: Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by means of X-ray powder diffraction. - Highlights: • Chemical compatibility between melilite-type gallate and cathodes for SOFCs up to 1573 K. • No reactivity observed between La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Reactivity observed between La{sub 0.80}Sr{sub 0.20}MnO{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Significant reactivity observed between La{sub 2}NiO{sub 4+d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}.

  10. Layered cathode materials for lithium ion rechargeable batteries

    DOEpatents

    Kang, Sun-Ho; Amine, Khalil

    2007-04-17

    A number of materials with the composition Li.sub.1+xNi.sub..alpha.Mn.sub..beta.Co.sub..gamma.M'.sub..delta.O.sub.2-- zF.sub.z (M'=Mg,Zn,Al,Ga,B,Zr,Ti) for use with rechargeable batteries, wherein x is between about 0 and 0.3, .alpha. is between about 0.2 and 0.6, .beta. is between about 0.2 and 0.6, .gamma. is between about 0 and 0.3, .delta. is between about 0 and 0.15, and z is between about 0 and 0.2. Adding the above metal and fluorine dopants affects capacity, impedance, and stability of the layered oxide structure during electrochemical cycling.

  11. Synthesis and characterization of cathode materials for lithium ion-rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Nieto Ramos, Santander

    Lithium intercalation materials are of special interest for cathodes in rechargeable lihium-ion batteries, because they are capable of reversibly intercalating lithium ions without altering the main unit. We developed a novel solution-based route for the synthesis of these lithium intercalates oxides. The first part of this work was devoted to the optimization of chemical solution process parameters in order to correlate their electrochemical properties. It was found that the lattice parameters and the crystallite size increase, whereas the lattice strain decreases with the increase in calcinations temperature. Powders annealed at 700°C for 15 h yielded best electrochemical performance. The electrochemical performance of substituted Li1.2Mn2O 4, Li1.2Mn1.8O4, Li1.2Cr 0.05Mn1.95O4, and Li1.2Cr0.05 Mn1.75O4 spinel electrodes in lithium cell has been studied. The electrochemical data showed that the Li and Cr dopant effect improves the cycleablility of spinel LiMn2O4 electrodes. The second part of this dissertation was devoted to improve the rate capabilities of these cathode materials by growing nano-size cathode particles and also by cation co-doping. Though the discharge capacity of these nano-crystalline cathodes was equivalent to their microcrystalline counterpart, these exhibited capacity fading in the 4V range. Through a combined X-ray diffraction, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses, we correlated the observed capacity fading with the onset of Jahn-Teller (J-T) distortion toward the end of the discharge in the cut-off limit between 4.2 and 3.2V. It was postulated that J-T distortion is the dominant fading mechanism of these nano-crystalline cathodes then by increasing the average oxidation state of the Mn ion in a virgin lithium manganate cathode, the onset of such distortion towards the end of the discharge could be delayed, and therefore, the cycleability of these cathodes could be improved. By synthesizing lithium

  12. Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

    DOEpatents

    Liang, Chengdu; Dudney, Nancy J; Howe, Jane Y

    2015-05-05

    The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

  13. Sulfur-based composite cathode materials for high-energy rechargeable lithium batteries.

    PubMed

    Wang, Jiulin; He, Yu-Shi; Yang, Jun

    2015-01-21

    There is currently an urgent demand for highly efficient energy storage and conversion systems. Due to its high theoretical energy density, low cost, and environmental compatibility, the lithium sulfur (Li-S) battery has become a typical representative of the next generation of electrochemical power sources. Various approaches have been explored to design and prepare sulfur cathode materials to enhance their electrochemical performance. This Research News article summarizes and compares different sulfur materials for Li-S batteries and particularly focuses on the fine structures, electrochemical performance, and electrode reaction mechanisms of pyrolyzed polyacrylo-nitrile sulfur (pPAN@S) and microporous-carbon/small-sulfur composite materials. PMID:25256595

  14. Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Howard, Wilmont F.; Spotnitz, Robert M.

    Lithium metal phosphates (olivines) are emerging as long-lived, safe cathode materials in Li-ion batteries. Nano-LiFePO 4 already appears in high-power applications, and LiMnPO 4 development is underway. Current and emerging Fe- and Mn-based intercalants, however, are low-energy producers compared to Ni and Co compounds. LiNiPO 4, a high voltage olivine, has the potential for superior energy output (>10.7 Wh in 18650 batteries), compared with commercial Li(Co,Ni)O 2 derivatives (up to 9.9 Wh). Speculative Co and Ni olivine cathode materials charged to above 4.5 V will require significant advances in electrolyte compositions and nanotechnology before commercialization. The major drivers toward 5 V battery chemistries are the inherent abuse tolerance of phosphates and the economic benefit of LiNiPO 4: it can produce 34% greater energy per dollar of cell material cost than LiAl 0.05Co 0.15Ni 0.8O 2, today's "standard" cathode intercalant in Li-ion batteries.

  15. Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

    SciTech Connect

    Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

    2013-06-01

    Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

  16. Comparison of Nonprecious Metal Cathode Materials for Methane Production by Electromethanogenesis

    PubMed Central

    2014-01-01

    In methanogenic microbial electrolysis cells (MMCs), CO2 is reduced to methane using a methanogenic biofilm on the cathode by either direct electron transfer or evolved hydrogen. To optimize methane generation, we examined several cathode materials: plain graphite blocks, graphite blocks coated with carbon black or carbon black containing metals (platinum, stainless steel or nickel) or insoluble minerals (ferrihydrite, magnetite, iron sulfide, or molybdenum disulfide), and carbon fiber brushes. Assuming a stoichiometric ratio of hydrogen (abiotic):methane (biotic) of 4:1, methane production with platinum could be explained solely by hydrogen production. For most other materials, however, abiotic hydrogen production rates were insufficient to explain methane production. At −600 mV, platinum on carbon black had the highest abiotic hydrogen gas formation rate (1600 ± 200 nmol cm–3 d–1) and the highest biotic methane production rate (250 ± 90 nmol cm–3 d–1). At −550 mV, plain graphite (76 nmol cm–3 d–1) performed similarly to platinum (73 nmol cm–3 d–1). Coulombic recoveries, based on the measured current and evolved gas, were initially greater than 100% for all materials except platinum, suggesting that cathodic corrosion also contributed to electromethanogenic gas production. PMID:24741468

  17. Comparison of Nonprecious Metal Cathode Materials for Methane Production by Electromethanogenesis.

    PubMed

    Siegert, Michael; Yates, Matthew D; Call, Douglas F; Zhu, Xiuping; Spormann, Alfred; Logan, Bruce E

    2014-04-01

    In methanogenic microbial electrolysis cells (MMCs), CO2 is reduced to methane using a methanogenic biofilm on the cathode by either direct electron transfer or evolved hydrogen. To optimize methane generation, we examined several cathode materials: plain graphite blocks, graphite blocks coated with carbon black or carbon black containing metals (platinum, stainless steel or nickel) or insoluble minerals (ferrihydrite, magnetite, iron sulfide, or molybdenum disulfide), and carbon fiber brushes. Assuming a stoichiometric ratio of hydrogen (abiotic):methane (biotic) of 4:1, methane production with platinum could be explained solely by hydrogen production. For most other materials, however, abiotic hydrogen production rates were insufficient to explain methane production. At -600 mV, platinum on carbon black had the highest abiotic hydrogen gas formation rate (1600 ± 200 nmol cm(-3) d(-1)) and the highest biotic methane production rate (250 ± 90 nmol cm(-3) d(-1)). At -550 mV, plain graphite (76 nmol cm(-3) d(-1)) performed similarly to platinum (73 nmol cm(-3) d(-1)). Coulombic recoveries, based on the measured current and evolved gas, were initially greater than 100% for all materials except platinum, suggesting that cathodic corrosion also contributed to electromethanogenic gas production.

  18. Selective Recovery of Lithium from Cathode Materials of Spent Lithium Ion Battery

    NASA Astrophysics Data System (ADS)

    Higuchi, Akitoshi; Ankei, Naoki; Nishihama, Syouhei; Yoshizuka, Kazuharu

    2016-10-01

    Selective recovery of lithium from four kinds of cathode materials, manganese-type, cobalt-type, nickel-type, and ternary-type, of spent lithium ion battery was investigated. In all cathode materials, leaching of lithium was improved by adding sodium persulfate (Na2S2O8) as an oxidant in the leaching solution, while the leaching of other metal ions (manganese, cobalt, and nickel) was significantly suppressed. Optimum leaching conditions, such as pH, temperature, amount of Na2S2O8, and solid/liquid ratio, for the selective leaching of lithium were determined for all cathode materials. Recovery of lithium from the leachate as lithium carbonate (Li2CO3) was then successfully achieved by adding sodium carbonate (Na2CO3) to the leachate. Optimum recovery conditions, such as pH, temperature, and amount of Na2CO3, for the recovery of lithium as Li2CO3 were determined for all cases. Purification of Li2CO3 was achieved by lixiviation in all systems, with purities of the Li2CO3 higher than 99.4%, which is almost satisfactory for the battery-grade purity of lithium.

  19. Comparison of Nonprecious Metal Cathode Materials for Methane Production by Electromethanogenesis.

    PubMed

    Siegert, Michael; Yates, Matthew D; Call, Douglas F; Zhu, Xiuping; Spormann, Alfred; Logan, Bruce E

    2014-04-01

    In methanogenic microbial electrolysis cells (MMCs), CO2 is reduced to methane using a methanogenic biofilm on the cathode by either direct electron transfer or evolved hydrogen. To optimize methane generation, we examined several cathode materials: plain graphite blocks, graphite blocks coated with carbon black or carbon black containing metals (platinum, stainless steel or nickel) or insoluble minerals (ferrihydrite, magnetite, iron sulfide, or molybdenum disulfide), and carbon fiber brushes. Assuming a stoichiometric ratio of hydrogen (abiotic):methane (biotic) of 4:1, methane production with platinum could be explained solely by hydrogen production. For most other materials, however, abiotic hydrogen production rates were insufficient to explain methane production. At -600 mV, platinum on carbon black had the highest abiotic hydrogen gas formation rate (1600 ± 200 nmol cm(-3) d(-1)) and the highest biotic methane production rate (250 ± 90 nmol cm(-3) d(-1)). At -550 mV, plain graphite (76 nmol cm(-3) d(-1)) performed similarly to platinum (73 nmol cm(-3) d(-1)). Coulombic recoveries, based on the measured current and evolved gas, were initially greater than 100% for all materials except platinum, suggesting that cathodic corrosion also contributed to electromethanogenic gas production. PMID:24741468

  20. Zero-Strain Na2FeSiO4 as Novel Cathode Material for Sodium-Ion Batteries.

    PubMed

    Li, Shouding; Guo, Jianghuai; Ye, Zhuo; Zhao, Xin; Wu, Shunqing; Mi, Jin-Xiao; Wang, Cai-Zhuang; Gong, Zhengliang; McDonald, Matthew J; Zhu, Zizhong; Ho, Kai-Ming; Yang, Yong

    2016-07-13

    A new cubic polymorph of sodium iron silicate, Na2FeSiO4, is reported for the first time as a cathode material for Na-ion batteries. It adopts an unprecedented cubic rigid tetrahedral open framework structure, i.e., F4̅3m, leading to a polyanion cathode material without apparent cell volume change during the charge/discharge processes. This cathode shows a reversible capacity of 106 mAh g(-1) and a capacity retention of 96% at 5 mA g(-1) after 20 cycles.

  1. Zero-Strain Na2FeSiO4 as Novel Cathode Material for Sodium-Ion Batteries.

    PubMed

    Li, Shouding; Guo, Jianghuai; Ye, Zhuo; Zhao, Xin; Wu, Shunqing; Mi, Jin-Xiao; Wang, Cai-Zhuang; Gong, Zhengliang; McDonald, Matthew J; Zhu, Zizhong; Ho, Kai-Ming; Yang, Yong

    2016-07-13

    A new cubic polymorph of sodium iron silicate, Na2FeSiO4, is reported for the first time as a cathode material for Na-ion batteries. It adopts an unprecedented cubic rigid tetrahedral open framework structure, i.e., F4̅3m, leading to a polyanion cathode material without apparent cell volume change during the charge/discharge processes. This cathode shows a reversible capacity of 106 mAh g(-1) and a capacity retention of 96% at 5 mA g(-1) after 20 cycles. PMID:27305627

  2. XAFS Study on Deterioration of Cathode Materials for Lithium-Ion Batteries

    SciTech Connect

    Nonaka, Takamasa; Okuda, Chikaaki; Kondo, Yasuhito; Seno, Yoshiki; Ukyo, Yoshio

    2007-02-02

    LiNi0.8CO0.15Al0.05O2, being one of the promising cathode materials for lithium-ion batteries, shows a distinct capacity fading after charge/discharge cycling and/or storage at high temperatures. The origin of these deteriorations has been explored by investigating the electronic and structural changes of the cathode material using X-ray absorption spectroscopy. Ni K-edge XAFS measurements were performed in two different modes: surface-sensitive conversion electron yield (CEY) mode and bulk-sensitive transmission mode. The Ni K-edge XANES showed that, after the cycle and aging tests, the Ni valences at the near-surface of the cathode particles became much lower than those in bulk. Whereas, the EXAFS showed that the bulk and surface-averaged Ni-O bond distances remained unchanged after the tests. These electronic and structural changes which occur prominently at near-surface are probably the main cause of the battery deterioration phenomenon.

  3. Nanostructured hybrid layered-spinel cathode material synthesized by hydrothermal method for lithium-ion batteries.

    PubMed

    Liu, Cong; Wang, Zhiyuan; Shi, Chunsheng; Liu, Enzuo; He, Chunnian; Zhao, Naiqin

    2014-06-11

    Nanostructured spinel LiMn1.5Ni0.5O4, layered Li1.5Mn0.75Ni0.25O2.5 and layered-spinel hybrid particles have been successfully synthesized by hydrothermal methods. It is found that the nanostructured hybrid cathode contains both spinel and layered components, which could be expressed as Li1.13Mn0.75Ni0.25O2.32. Diffraction-contrast bright-field (BF) and dark-field (DF) images illustrate that the hybrid cathode has well dispersed spinel component. Electrochemical measurements reveal that the first-cycle efficiency of the layered-spinel hybrid cathode is greatly improved (up to 90%) compared with that of the layered material (71%) by integrating spinel component. Our investigation demonstrates that the spinel containing hybrid material delivers a high capacity of 240 mAh g(-1) with good cycling stability between 2.0 and 4.8 V at a current rate of 0.1 C.

  4. Deciphering the thermal behavior of lithium rich cathode material by in situ X-ray diffraction technique

    NASA Astrophysics Data System (ADS)

    Muhammad, Shoaib; Lee, Sangwoo; Kim, Hyunchul; Yoon, Jeongbae; Jang, Donghyuk; Yoon, Jaegu; Park, Jin-Hwan; Yoon, Won-Sub

    2015-07-01

    Thermal stability is one of the critical requirements for commercial operation of high energy lithium-ion batteries. In this study, we use in situ X-ray diffraction technique to elucidate the thermal degradation mechanism of 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2 lithium rich cathode material in the absence and presence of electrolyte to simulate the real life battery conditions and compare its thermal behavior with the commercial LiNi0.33Co0.33Mn0.33O2 cathode material. We show that the thermal induced phase transformations in delithiated lithium rich cathode material are much more intense compared to similar single phase layered cathode material in the presence of electrolyte. The structural changes in both cathode materials with the temperature rise follow different trends in the absence and presence of electrolyte between 25 and 600 °C. Phase transitions are comparatively simple in the absence of electrolyte, the fully charged lithium rich cathode material demonstrates better thermal stability by maintaining its phase till 379 °C, and afterwards spinel structure is formed. In the presence of electrolyte, however, the spinel structure appears at 207 °C, subsequently it transforms to rock salt type cubic phase at 425 °C with additional metallic, metal fluoride, and metal carbonate phases.

  5. Electricity generation and bivalent copper reduction as a function of operation time and cathode electrode material in microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Wu, Dan; Huang, Liping; Quan, Xie; Li Puma, Gianluca

    2016-03-01

    The performance of carbon rod (CR), titanium sheet (TS), stainless steel woven mesh (SSM) and copper sheet (CS) cathode materials are investigated in microbial fuel cells (MFCs) for simultaneous electricity generation and Cu(II) reduction, in multiple batch cycle operations. After 12 cycles, the MFC with CR exhibits 55% reduction in the maximum power density and 76% increase in Cu(II) removal. In contrast, the TS and SSM cathodes at cycle 12 show maximum power densities of 1.7 (TS) and 3.4 (SSM) times, and Cu(II) removal of 1.2 (TS) and 1.3 (SSM) times higher than those observed during the first cycle. Diffusional resistance in the TS and SSM cathodes is found to appreciably decrease over time due to the copper deposition. In contrast to CR, TS and SSM, the cathode made with CS is heavily corroded in the first cycle, exhibiting significant reduction in both the maximum power density and Cu(II) removal at cycle 2, after which the performance stabilizes. These results demonstrate that the initial deposition of copper on the cathodes of MFCs is crucial for efficient and continuous Cu(II) reduction and electricity generation over prolonged time. This effect is closely associated with the nature of the cathode material. Among the materials examined, the SSM is the most effective and inexpensive cathode for practical use in MFCs.

  6. Is alpha-V2O5 a cathode material for Mg insertion batteries?

    NASA Astrophysics Data System (ADS)

    Sa, Niya; Wang, Hao; Proffit, Danielle L.; Lipson, Albert L.; Key, Baris; Liu, Miao; Feng, Zhenxing; Fister, Timothy T.; Ren, Yang; Sun, Cheng-Jun; Vaughey, John T.; Fenter, Paul A.; Persson, Kristin A.; Burrell, Anthony K.

    2016-08-01

    When designing a high energy density battery, one of the critical features is a high voltage, high capacity cathode material. In the development of Mg batteries, oxide cathodes that can reversibly intercalate Mg, while at the same time being compatible with an electrolyte that can deposit Mg reversibly are rare. Herein, we report the compatibility of Mg anodes with α-V2O5 by employing magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolytes at very low water levels. Electrolytes that contain a high water level do not reversibly deposit Mg, but interestingly these electrolytes appear to enable much higher capacities for an α-V2O5 cathode. Solid state NMR indicates that the major source of the higher capacity in high water content electrolytes originates from reversible proton insertion. In contrast, we found that lowering the water level of the magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte is critical to achieve reversible Mg deposition and direct evidence for reversible Mg intercalation is shown. Findings we report here elucidate the role of proton intercalation in water-containing electrolytes and clarify numerous conflicting reports of Mg insertion into α-V2O5.

  7. Synthesis, strctural and electrochemical characterizations of lithium- manganese- rich composite cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Dapeng

    The electrification trend for transportation systems requires alternative cathode materials to LiCoO2 with improved safety, lowered cost and extended cycle life. Lithium- manganese- rich composite cathode materials, which can be presented in a two component notation as xLi2MnO3·(1-x)LiMO 2, (M= Ni, Co or Mn) have superior cost and energy density advantages. These cathode materials have shown success in laboratory scale experiments, but are still facing challenges such as voltage fade, moderate rate capacity and tap density for commercialization. The synthesis of precursors with high packing density and suitable physical properties is critical to achieve high energy density as well as the other acceptable electrochemical performance for the next generation lithium ion batteries. The aim of this study is to correlate the electrochemical properties of materials to their structural, morphological, and physical properties by coordinating the science of synthesis with the science of function, in order to enable the use of these compounds in vehicle technologies. Three different precursors including carbonate, hydroxide and oxalate were synthesized by co-precipitation reactions using continuous stirred tank reactor (CSTR) under various conditions. Research focused on areas such as nucleation and growth mechanisms, synthesis optimizations, and intrinsic limitations of each co-precipitation method. A combination of techniques such as PSA, BET, SEM, EDX FIB, TEM, Raman, FTIR, TGA-DSC, XRD, and ICP-MS, as well as electrochemical test methods such as cycling, CV, EIS and HPPC tests were used in correlation with each other in order to deepen our understanding to these materials. Related topics such as the composite structure formation process during the solid state reaction, lithium and nickel content effects on the cathode properties were also discussed. Additionally, the side reactions between the active materials and electrolyte as a result of the high charge potential were

  8. Electrochemical properties of lithium polymer batteries with doped polyaniline as cathode material

    SciTech Connect

    Manuel, James; Kim, Jae-Kwang; Matic, Aleksandar; Jacobsson, Per; Chauhan, Ghanshyam S.; Ha, Jong Keun; Cho, Kwon-Koo; Ahn, Jou-Hyeon

    2012-10-15

    Graphical abstract: -- Abstract: Polyaniline (PANI) was doped with different lithium salts such as LiPF{sub 6} and LiClO{sub 4} and evaluated as cathode-active material for application in room-temperature lithium batteries. The doped PANI was characterized by FTIR and XPS measurements. In the FTIR spectra, the characteristic peaks of PANI are shifted to lower bands as a consequence of doping, and it is more shifted in the case of PANI doped with LiPF{sub 6}. The cathodes prepared using PANI doped with LiPF{sub 6} and LiClO{sub 4} delivered initial discharge capacities of 125 mAh g{sup −1} and 112 mAh g{sup −1} and stable reversible capacities of 114 mAh g{sup −1} and 81 mAh g{sup −1}, respectively, after 10 charge–discharge cycles. The cells were also tested using polymer electrolyte, which delivered highest discharge capacities of 142.6 mAh g{sup −1} and 140 mAh g{sup −1} and stable reversible capacities of 117 mAh g{sup −1} and 122 mAh g{sup −1} for PANI-LiPF{sub 6} and PANI-LiClO{sub 4}, respectively, after 10 cycles. The cathode prepared with LiPF{sub 6} doped PANI shows better cycling performance and stability as compared to the cathode prepared with LiClO{sub 4} doped PANI using both liquid and polymer electrolytes.

  9. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

    DOE PAGES

    Lin, Feng; Xin, Huolin L.; Nordlund, Dennis; Li, Yuyi; Quan, Matthew K.; Cheng, Lei; Weng, Tsu -Chien; Liu, Yijin; Doeff, Marca M.

    2016-01-11

    Controlling surface and interfacial properties of battery materials is key to improving performance in rechargeable Li-ion devices. Surface reconstruction from a layered to a rock salt structure in metal oxide cathode materials is commonly observed and results in poor high-voltage cycling performance, impeding attempts to improve energy density. Hierarchically structured LiNi0.4Mn0.4Co0.2O2 (NMC-442) spherical powders, made by spray pyrolysis, exhibit local elemental distribution gradients that deviate from the global NMC-442 composition; specifically, they are Ni-rich and Mn-poor at particle surfaces. These materials demonstrate improved Coulombic efficiencies, discharge capacities, and high-voltage capacity retention in lithium half-cell configurations. The subject powders show superiormore » resistance against surface reconstruction due to the tailored surface chemistry, compared to conventional NMC-442 materials. This paves the way towards the development of a new generation of robust and stable high-energy NMC cathodes for Li-ion batteries.« less

  10. Rational design of novel cathode materials in solid oxide fuel cells using first-principles simulations

    NASA Astrophysics Data System (ADS)

    Choi, YongMan; Lin, M. C.; Liu, Meilin

    The search for clean and renewable sources of energy represents one of the most vital challenges facing us today. Solid oxide fuel cells (SOFCs) are among the most promising technologies for a clean and secure energy future due to their high energy efficiency and excellent fuel flexibility (e.g., direct utilization of hydrocarbons or renewable fuels). To make SOFCs economically competitive, however, development of new materials for low-temperature operation is essential. Here we report our results on a computational study to achieve rational design of SOFC cathodes with fast oxygen reduction kinetics and rapid ionic transport. Results suggest that surface catalytic properties are strongly correlated with the bulk transport properties in several material systems with the formula of La 0.5Sr 0.5BO 2.75 (where B = Cr, Mn, Fe, or Co). The predictions seem to agree qualitatively with available experimental results on these materials. This computational screening technique may guide us to search for high-efficiency cathode materials for a new generation of SOFCs.

  11. Effect of the cathode material on the removal of nitrates by electrolysis in non-chloride media.

    PubMed

    Lacasa, Engracia; Cañizares, Pablo; Llanos, Javier; Rodrigo, Manuel A

    2012-04-30

    In this work, the effect of the cathode material (conductive diamond, stainless steel, silicon carbide, graphite or lead) and the current density (150-1400 A m(-2)) on the removal of nitrates from aqueous solutions is studied by electrolysis in non-divided electrochemical cells equipped with conductive diamond anodes, using sodium sulphate as the electrolyte. The results show that the cathode material very strongly influences both the process performance and the product distribution. The main products obtained are gaseous nitrogen (NO, N(2)O and NO(2)) and ammonium ions. Nitrate removal follows first order kinetics, which indicates that the electrolysis process is controlled by mass transfer. Furthermore, the stainless steel and graphite cathodes show a great selectivity towards the production of ammonium ions, whereas the silicon carbide cathode leads to the highest formation of gaseous nitrogen, which production is promoted at low current densities.

  12. Synthesis of LiNiO2 cathode materials with homogeneous Al doping at the atomic level

    SciTech Connect

    Liu, Zengcai; Zhen, Honghe; Kim, Yoongu; Liang, Chengdu

    2011-01-01

    Aluminum doped LiNiO2 cathode materials are synthesized by using Raney nickel as the starting material. The structure and composition are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with elemental mapping. The lithium deficiency is analyzed by Rieveld refinement. The initial capacity and retention of capacity are correlated to the lithium deficiency of the resulting cathode material. Using strong oxidant of Li2O2 in the synthesis results in materials with improved electrochemical cyclability. The improvement is related to the diminishing of lithium deficiency in strong oxidizing synthesis conditions.

  13. Surface structure evolution of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Yingchun, Lyu; Yali, Liu; Lin, Gu

    2016-01-01

    Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the evolution of the surface structure of the cathode materials at different states of the pristine, storage and electrochemical reactions are summarized. The main methods for the surface modification are also introduced. Project supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030200) and the National Basic Research Program of China (Grant Nos. 2014CB921002 and 2012CB921702).

  14. Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

    PubMed

    Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

    2016-01-11

    As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries.

  15. Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

    PubMed

    Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

    2016-01-11

    As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries. PMID:26609636

  16. Covalently Functionalized Graphene by Radical Polymers for Graphene-Based High-Performance Cathode Materials.

    PubMed

    Li, Yongjun; Jian, Zukai; Lang, Meidong; Zhang, Chunming; Huang, Xiaoyu

    2016-07-13

    Polymer-functionalized graphene sheets play an important role in graphene-containing composite materials. Herein, functionalized graphene sheets covalently linked with radical polymer, graphene-graft-poly(2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl methacrylate) (G-g-PTMA), were prepared via surface-initiated atom transfer radical polymerization (SI-ATRP). A composite cathode with G-g-PTMA as major active material and reduced graphene oxide (RGO) as conductive additive was fabricated via a simple dispersing-depositing process, and this composite cathode exhibited a relatively high specific capacity up to 466 mAh g(-1) based on the mass of PTMA, which is much higher than the theoretical capacity of PTMA. This extraordinary electrochemical performance is attributed to the fast one-electron redox reaction of G-g-PTMA and surface Faradaic reaction of RGO boosted by G-g-PTMA, which suggested that G-g-PTMA sheets play a dual role in the composite materials, that is, on the one hand provided the fast one-electron redox reaction of PTMA and on the other hand worked as nanofiller for facilitating the surface Faradaic reaction-based lithium storage of RGO. PMID:27328986

  17. Evaluating the economic viability of a material recovery system: the case of cathode ray tube glass.

    PubMed

    Gregory, Jeremy R; Nadeau, Marie-Claude; Kirchain, Randolph E

    2009-12-15

    This paper presents an analysis of the material recovery system for leaded glass from cathode ray tubes (CRTs) using a dynamic material flow analysis. In particular, the global mass flow of primary and secondary CRT glass and the theoretical capacities for using secondary CRT glass to make new CRT glass are analyzed. The global mass flow analysis indicates that the amount of new glass required is decreasing, but is much greater than the amount of secondary glass collected, which is increasing. The comparison of the ratio of secondary glass collected to the amount of new glass required from the mass flow analysis indicates that the material recovery system is sustainable for the foreseeable future. However, a prediction of the time at which the market for secondary glass will collapse due to excess capacity is not possible at the moment due to several sources of uncertainty.

  18. Synthesis and characterization of cathode, anode and electrolyte materials for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Yang, Shoufeng

    Two new classes of cathode materials were studied: iron phosphate/sulfate materials and layered manganese oxides, both of which are low cost and had shown some potential. The first class of materials have poor conductivity and cyclability. I studied a number of methods for increasing the conductivity, and determined that grinding the material with carbon black was as effective as special in-situ coatings. The optimum carbon loading was determined to be between 6 and 15 wt%. Too much carbon reduces the volumetric energy density, whereas too little significantly increased cell polarization (reduced the rate of reaction). The kinetic and thermodynamic stability of LiFePO 4 was also studied and it was determined that over discharge protection will be needed as irreversible Li3PO4 can be formed at low potentials. A novel hydrothermal synthesis method was developed, but the significant level of Fe on the Li site reduces the reaction rate too much. In the case of the layered manganese oxide, cation substitution with Co and Ni is found to be effective in avoiding Jahn-Teller effects and improving electrochemistry. A wide range of tin compounds have been suggested as lithium storage media for advanced anode materials, as tin can store over 4 Li per Sn atom. Lithium hexafluorophosphate, LiPF6, is presently the salt of choice for LiCoO2 batteries, but it is expensive and dissolves some manganese compounds. The lithium bis(oxolato)borate (BOB) salt was recently reported, and I made a study of its use in cells with the LiFePO4 cathode and the tin anode. During its synthesis, it became clear that LiBOB is very reactive with many solvents, and these complexes were characterized to better understand this new material. In LiBOB the lithium is five coordinated, an unstable configuration for the lithium ion so that water and many other solvents rapidly react to make a six coordination. Only in the case of ethylene carbonate was the lithium found to be four coordinated. The Li

  19. Zinc/air cell cathode

    NASA Astrophysics Data System (ADS)

    McEvoy, J. J.

    1986-04-01

    This invention relates to a cathode for an air depolarized cell in which the hydrophobic catalytic cathode contains or in integrally drophobi catalytic cathode contains or is integrally coated with, on the surface adjacent the cell separator, an absorbent material such as the gelling material used in the anode. The absorbent material, integrated with the cathode surface, adheres the separator to the cathode thereby preventing delamination and provides an electrolyte reservoir for the hydrophobic cathode.

  20. In Situ X-ray Diffraction Studies of Cathode Materials in Lithium Batteries

    SciTech Connect

    Yang, X. Q.; Sun, X.; McBreen, J.; Mukerjee, S.; Gao, Yuan; Yakovleva, M. V.; Xing, X. K.; Daroux, M. L.

    1998-11-01

    There is an increasing interest in lithiated transition metal oxides because of their use as cathodes in lithium batteries. LiCoO{sub 2}, LiNiO{sub 2} and LiMn{sub 2}O{sub 4} are the three most widely used and studied materials, At present, although it is relative expensive and toxic, LiCoO{sub 2} is the material of choice in commercial lithium ion batteries because of its ease of manufacture, better thermal stability and cycle life. However, the potential use of lithium ion batteries with larger capacity for power tools and electric vehicles in the future will demand new cathode materials with higher energy density, lower cost and better thermal stability. LiNiO{sub 2} is isostructural with LiCoO{sub 2}. It offers lower cost and high energy density than LiCoO{sub 2}. However, it has much poorer thermal stability than LiCoO{sub 2}, in the charged (delithiated) state. Co, Al, and other elements have been used to partially replace Ni in LiNiO{sub 2} system in order to increase the thermal stability. LiMn{sub 2}O{sub 4} has the highest thermal stability and lowest cost and toxicity. However, the low energy density and poor cycle life at elevated temperature are the major obstacles for this material. In order to develop safer, cheaper, and better performance cathode materials, the in-depth understanding of the relationships between the thermal stability and structure, performance and structure are very important. The performance here includes energy density and cycle life of the cathode materials. X-ray diffraction (XRD) is one of the most powerful tools to study these relationships. The pioneer ex situ XRD work on cathode materials for lithium batteries was done by Ohzuku. His XRD studies on LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2}, LiNi{sub 0.5}Co{sub 0.5}O{sub 2}, and LiAl{sub x}Ni{sub 1-x}O{sub 2} cathodes at different states of charge have provided important guidelines for the development of these new materials. However, the kinetic nature of the battery

  1. Development and characterization of novel cathode materials for molten carbonate fuel cell

    NASA Astrophysics Data System (ADS)

    Giorgi, L.; Carewska, M.; Patriarca, M.; Scaccia, S.; Simonetti, E.; Dibartolomeo, A.

    1994-04-01

    In the development of molten carbonate fuel cell (MCFC) technology, the corrosion of materials is a serious problem for long-term operation. Indeed, slow dissolution of lithiated-NiO cathode in molten carbonates is the main obstacle for the commercialization of MCFCs. In the search of new, more stable, cathode materials, alternative compounds such as LiFeO2, Li2MnO3, and La(1-x)Sr(x)CoO3 are presently under investigation to replace the currently used lithiated-NiO. The aim of the present work was to investigate the possibility to produce electrode based on LiCoO2, a promising cathode material. At first, Li(x)CoO2 powder samples (0.8 less than x less than 1.1) were made by thermal decomposition of carbonate precursors in air. The synthesis processes were monitored by thermal analysis (TGA, DTA). The calcined and sintered powder samples were characterized by x ray diffraction (XRD) andatomic absorption spectrophotometry (F-AAS). A single phase was detected in all the samples, without any change in crystal structure as a function of lithium content. Porous sintered electrodes were prepared starting from lithium cobaltite powders mixed with different pore-formers by cold pressing and sintering. A bimodal pore-size distribution with a mean pore diameter in the range of 0.15 to 8 micron, a surface area of 2 to 12 sq m/g and a porosity of 10 to 65%, determined by the Hg-intrusion technique, were observed in all the materials. Conductivity measurements were carried out in the temperature range of 500-700 C, in air. The influence of the deviations from stoichiometry on the electronic properties was determined, the conductivity value of the stoichiometric compound being the lowest. A linear relationship between the electronic conductivity and the sample porosity was found. Solubility testing of the materials was carried out to evaluate their chemical stability in the electrolyte. The sampling method (F-AAS) and square wave voltammetry (SWV) were used to determine the

  2. Accelerated discovery of cathode materials with prolonged cycle life for lithium-ion battery.

    PubMed

    Nishijima, Motoaki; Ootani, Takuya; Kamimura, Yuichi; Sueki, Toshitsugu; Esaki, Shogo; Murai, Shunsuke; Fujita, Koji; Tanaka, Katsuhisa; Ohira, Koji; Koyama, Yukinori; Tanaka, Isao

    2014-01-01

    Large-scale battery systems are essential for efficiently utilizing renewable energy power sources from solar and wind, which can generate electricity only intermittently. The use of lithium-ion batteries to store the generated energy is one solution. A long cycle life is critical for lithium-ion battery when used in these applications; this is different from portable devices which require 1,000 cycles at most. Here we demonstrate a novel co-substituted lithium iron phosphate cathode with estimated 70%-capacity retention of 25,000 cycles. This is found by exploring a wide chemical compositional space using density functional theory calculations. Relative volume change of a compound between fully lithiated and delithiated conditions is used as the descriptor for the cycle life. On the basis of the results of the screening, synthesis of selected materials is targeted. Single-phase samples with the required chemical composition are successfully made by an epoxide-mediated sol-gel method. The optimized materials show excellent cycle-life performance as lithium-ion battery cathodes.

  3. Heteroaromatic organic compound with conjugated multi-carbonyl as cathode material for rechargeable lithium batteries

    PubMed Central

    Lv, Meixiang; Zhang, Fen; Wu, Yiwen; Chen, Mujuan; Yao, Chunfeng; Nan, Junmin; Shu, Dong; Zeng, Ronghua; Zeng, Heping; Chou, Shu-Lei

    2016-01-01

    The heteroaromatic organic compound, N,N’-diphenyl-1,4,5,8-naphthalenetetra- carboxylic diimide (DP-NTCDI-250) as the cathode material of lithium batteries is prepared through a simple one-pot N-acylation reaction of 1,4,5,8-naphthalenetetra-carboxylic dianhydride (NTCDA) with phenylamine (PA) in DMF solution followed by heat treatment in 250 °C. The as prepared sample is characterized by the combination of elemental analysis, NMR, FT-IR, TGA, XRD, SEM and TEM. The electrochemical measurements show that DP-NTCDI-250 can deliver an initial discharge capacity of 170 mAh g−1 at the current density of 25 mA g−1. The capacity of 119 mAh g−1 can be retained after 100 cycles. Even at the high current density of 500 mA g−1, its capacity still reaches 105 mAh g−1, indicating its high rate capability. Therefore, the as-prepared DP-NTCDI-250 could be a promising candidate as low cost cathode materials for lithium batteries. PMID:27064938

  4. Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching.

    PubMed

    Ku, Heesuk; Jung, Yeojin; Jo, Minsang; Park, Sanghyuk; Kim, Sookyung; Yang, Donghyo; Rhee, Kangin; An, Eung-Mo; Sohn, Jeongsoo; Kwon, Kyungjung

    2016-08-01

    As the production and consumption of lithium ion batteries (LIBs) increase, the recycling of spent LIBs appears inevitable from an environmental, economic and health viewpoint. The leaching behavior of Ni, Mn, Co, Al and Cu from treated cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles, is investigated with ammoniacal leaching agents based on ammonia, ammonium carbonate and ammonium sulfite. Ammonium sulfite as a reductant is necessary to enhance leaching kinetics particularly in the ammoniacal leaching of Ni and Co. Ammonium carbonate can act as a pH buffer so that the pH of leaching solution changes little during leaching. Co and Cu can be fully leached out whereas Mn and Al are hardly leached and Ni shows a moderate leaching efficiency. It is confirmed that the cathode active materials are a composite of LiMn2O4, LiCoxMnyNizO2, Al2O3 and C while the leach residue is composed of LiNixMnyCozO2, LiMn2O4, Al2O3, MnCO3 and Mn oxides. Co recovery via the ammoniacal leaching is believed to gain a competitive edge on convenitonal acid leaching both by reducing the sodium hydroxide expense for increasing the pH of leaching solution and by removing the separation steps of Mn and Al. PMID:27060219

  5. Heteroaromatic organic compound with conjugated multi-carbonyl as cathode material for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Lv, Meixiang; Zhang, Fen; Wu, Yiwen; Chen, Mujuan; Yao, Chunfeng; Nan, Junmin; Shu, Dong; Zeng, Ronghua; Zeng, Heping; Chou, Shu-Lei

    2016-04-01

    The heteroaromatic organic compound, N,N’-diphenyl-1,4,5,8-naphthalenetetra- carboxylic diimide (DP-NTCDI-250) as the cathode material of lithium batteries is prepared through a simple one-pot N-acylation reaction of 1,4,5,8-naphthalenetetra-carboxylic dianhydride (NTCDA) with phenylamine (PA) in DMF solution followed by heat treatment in 250 °C. The as prepared sample is characterized by the combination of elemental analysis, NMR, FT-IR, TGA, XRD, SEM and TEM. The electrochemical measurements show that DP-NTCDI-250 can deliver an initial discharge capacity of 170 mAh g‑1 at the current density of 25 mA g‑1. The capacity of 119 mAh g‑1 can be retained after 100 cycles. Even at the high current density of 500 mA g‑1, its capacity still reaches 105 mAh g‑1, indicating its high rate capability. Therefore, the as-prepared DP-NTCDI-250 could be a promising candidate as low cost cathode materials for lithium batteries.

  6. Kinetic modelling of molten carbonate fuel cells: Effects of cathode water and electrode materials

    NASA Astrophysics Data System (ADS)

    Arato, E.; Audasso, E.; Barelli, L.; Bosio, B.; Discepoli, G.

    2016-10-01

    Through previous campaigns the authors developed a semi-empirical kinetic model to describe MCFC performance for industrial and laboratory simulation. Although effective in a wide range of operating conditions, the model was validated for specific electrode materials and dry feeding cathode compositions. The new aim is to prove that with appropriate improvements it is possible to apply the model to MCFC provided by different suppliers and to new sets of reactant gases. Specifically, this paper describes the procedures to modify the model to switch among different materials and identify a new parameter taking into account the effects of cathode water vapour. The new equation is integrated as the kinetic core within the SIMFC (SIMulation of Fuel Cells) code, an MCFC 3D model set up by the PERT group of the University of Genova, for reliability test. Validation is performed using data collected through tests carried out at the University of Perugia using single cells. The results are discussed giving examples of the simulated performance with varying operating conditions. The final formulation average percentage error obtained for all the simulated cases with respect to experimental results is maintained around 1%, despite the difference between the basic and the new conditions and facilities.

  7. A mesoporous carbon–sulfur composite as cathode material for high rate lithium sulfur batteries

    SciTech Connect

    Choi, Hyunji; Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Hyo-Jun; Kim, Ki-Won; Cho, Kwon-Koo; Ahn, Jou-Hyeon

    2014-10-15

    Highlights: • CMK-3 mesoporous carbon was synthesized as conducting reservoir for housing sulfur. • Sulfur/CMK-3 composites were prepared by two-stage thermal treatment. • The composite at 300 °C for 20 h shows improved electrochemical properties. - Abstract: Sulfur composite was prepared by encapsulating sulfur into CMK-3 mesoporous carbon with different heating times and then used as the cathode material for lithium sulfur batteries. Thermal treatment at 300 °C plays an important role in the sulfur encapsulation process. With 20 h of heating time, a portion of sulfur remained on the surface of carbon, whereas with 60 h of heating time, sulfur is confined deeply in the small pores of carbon that cannot be fully exploited in the redox reaction, thus causing low capacity. The S/CMK-3 composite with thermal treatment for 40 h at 300 °C contained 51.3 wt.% sulfur and delivered a high initial capacity of 1375 mA h g{sup −1} at 0.1 C. Moreover, it showed good capacity retention of 704 mA h g{sup −1} at 0.1 C and 578 mA h g{sup −1} at 2 C even after 100 cycles, which proves its potential as a cathode material for high capability lithium sulfur batteries.

  8. Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching.

    PubMed

    Ku, Heesuk; Jung, Yeojin; Jo, Minsang; Park, Sanghyuk; Kim, Sookyung; Yang, Donghyo; Rhee, Kangin; An, Eung-Mo; Sohn, Jeongsoo; Kwon, Kyungjung

    2016-08-01

    As the production and consumption of lithium ion batteries (LIBs) increase, the recycling of spent LIBs appears inevitable from an environmental, economic and health viewpoint. The leaching behavior of Ni, Mn, Co, Al and Cu from treated cathode active materials, which are separated from a commercial LIB pack in hybrid electric vehicles, is investigated with ammoniacal leaching agents based on ammonia, ammonium carbonate and ammonium sulfite. Ammonium sulfite as a reductant is necessary to enhance leaching kinetics particularly in the ammoniacal leaching of Ni and Co. Ammonium carbonate can act as a pH buffer so that the pH of leaching solution changes little during leaching. Co and Cu can be fully leached out whereas Mn and Al are hardly leached and Ni shows a moderate leaching efficiency. It is confirmed that the cathode active materials are a composite of LiMn2O4, LiCoxMnyNizO2, Al2O3 and C while the leach residue is composed of LiNixMnyCozO2, LiMn2O4, Al2O3, MnCO3 and Mn oxides. Co recovery via the ammoniacal leaching is believed to gain a competitive edge on convenitonal acid leaching both by reducing the sodium hydroxide expense for increasing the pH of leaching solution and by removing the separation steps of Mn and Al.

  9. Curly MnOx nanomembranes as cathode materials for rechargeable lithium-oxygen battery systems

    NASA Astrophysics Data System (ADS)

    Lu, Xueyi; Si, Wenping; Sun, Xiaolei; Deng, Junwen; Xi, Lixia; Liu, Bo; Yan, Chenglin; Schmidt, Oliver G.

    2015-11-01

    Two-dimensional MnOx nanomembranes prepared by electron beam evaporation are rolled up into three-dimensional hybrid micro/nano-tubes by strain release. The material is characterized with Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cyclic voltammetry and used as the cathode catalysts for lithium-oxygen (Li-O2) batteries. The Li-O2 battery using such curly MnOx nanomembranes as the cathode delivers a specific discharge capacity of 4610 mAh gC-1 at a current density of 70 mA gC-1 which is higher than that of carbon black. Moreover, the MnOx nanomembrane electrode gains improved stability, being capable of cycling 112 times at a current density of 200 mA gC-1 . The encouraging performance is ascribed to the unique superiorities of nanomembranes and those inner oxygen vacancies, indicating that nanomembranes are promising materials for Li-O2 batteries.

  10. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  11. Gas evolution from cathode materials: A pathway to solvent decomposition concomitant to SEI formation.

    SciTech Connect

    Browning, Katie L; Baggetto, Loic; Unocic, Raymond R; Dudney, Nancy J; Veith, Gabriel M

    2013-01-01

    This work reports a method to explore the catalytic reactivity of electrode surfaces towards the decomposition of carbonate solvents [ethylene carbonate (EC), dimethyl carbonate (DMC), and EC/DMC]. We show that the decomposition of a 1:1 wt% EC/DMC mixture is accelerated over certain commercially available LiCoO2 materials resulting in the formation of CO2 while over pure EC or DMC the reaction is much slower or negligible. The solubility of the produced CO2 in carbonate solvents is high (0.025 grams/mL) which masks the effect of electrolyte decomposition during storage or use. The origin of this decomposition is not clear but it is expected to be present on other cathode materials and may affect the analysis of SEI products as well as the safety of Li-ion batteries.

  12. Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes’ effects on thermal & cycling stability

    NASA Astrophysics Data System (ADS)

    Xiqian, Yu; Enyuan, Hu; Seongmin, Bak; Yong-Ning, Zhou; Xiao-Qing, Yang

    2016-01-01

    Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems. Project supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies (Grant No. DE-SC0012704).

  13. Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes' effects on thermal & cycling stability

    DOE PAGES

    Yu, Xiqian; Hu, Enyuan; Bak, Seongmin; Zhou, Yong -Ning; Yang, Xiao -Qing

    2015-12-07

    Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. Furthermore, we also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue. As a result, it is widely accepted that the thermal instability of themore » cathodes is one of the most critical factors in thermal runaway and related safety problems.« less

  14. Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes' effects on thermal & cycling stability

    SciTech Connect

    Yu, Xiqian; Hu, Enyuan; Bak, Seongmin; Zhou, Yong -Ning; Yang, Xiao -Qing

    2015-12-07

    Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. Furthermore, we also discuss applying the information about heat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue. As a result, it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems.

  15. Excellent cycling stability and superior rate capability of a graphene-amorphous FePO4 porous nanowire hybrid as a cathode material for sodium ion batteries.

    PubMed

    Yang, Gaoliang; Ding, Bing; Wang, Jie; Nie, Ping; Dou, Hui; Zhang, Xiaogang

    2016-04-28

    A porous nanowire material consisting of graphene-amorphous FePO4 was investigated as an advanced cathode material for sodium ion batteries for large-scale applications. This hybrid cathode material showed excellent cycling performance and superior rate capability, which were attributed to the porous nanowire structure and the existence of graphene. PMID:27064740

  16. Excellent cycling stability and superior rate capability of a graphene-amorphous FePO4 porous nanowire hybrid as a cathode material for sodium ion batteries.

    PubMed

    Yang, Gaoliang; Ding, Bing; Wang, Jie; Nie, Ping; Dou, Hui; Zhang, Xiaogang

    2016-04-28

    A porous nanowire material consisting of graphene-amorphous FePO4 was investigated as an advanced cathode material for sodium ion batteries for large-scale applications. This hybrid cathode material showed excellent cycling performance and superior rate capability, which were attributed to the porous nanowire structure and the existence of graphene.

  17. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

    NASA Astrophysics Data System (ADS)

    Lin, Feng; Nordlund, Dennis; Li, Yuyi; Quan, Matthew K.; Cheng, Lei; Weng, Tsu-Chien; Liu, Yijin; Xin, Huolin L.; Doeff, Marca M.

    2016-01-01

    In technologically important LiNi1-x-yMnxCoyO2 cathode materials, surface reconstruction from a layered to a rock-salt structure is commonly observed under a variety of operating conditions, particularly in Ni-rich compositions. This phenomenon contributes to poor high-voltage cycling performance, impeding attempts to improve the energy density by widening the potential window at which these electrodes operate. Here, using advanced nano-tomography and transmission electron microscopy techniques, we show that hierarchically structured LiNi0.4Mn0.4Co0.2O2 spherical particles, made by a simple spray pyrolysis method, exhibit local elemental segregation such that surfaces are Ni-poor and Mn-rich. The tailored surfaces result in superior resistance to surface reconstruction compared with those of conventional LiNi0.4Mn0.4Co0.2O2, as shown by soft X-ray absorption spectroscopy experiments. The improved high-voltage cycling behaviour exhibited by cells containing these cathodes demonstrates the importance of controlling LiNi1-x-yMnxCoyO2 surface chemistry for successful development of high-energy lithium ion batteries.

  18. Pulsed mode cathode

    NASA Technical Reports Server (NTRS)

    Myers, Roger M. (Inventor); Rawlin, Vinvent K. (Inventor)

    1994-01-01

    A cathode in an MPD thruster has an internal heater and utilizes low work function material. The cathode is preheated to operating temperature, and then the thruster is fired by discharging a capacitor bank in a pulse forming network.

  19. Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries

    PubMed Central

    Antipov, Evgeny V.; Khasanova, Nellie R.; Fedotov, Stanislav S.

    2015-01-01

    To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4)n− and F−] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications. PMID:25610630

  20. Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries.

    PubMed

    Antipov, Evgeny V; Khasanova, Nellie R; Fedotov, Stanislav S

    2015-01-01

    To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4) (n-) and F(-)] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications.

  1. Preparation and Characterization of Grain Size Controlled LaB6 Polycrystalline Cathode Material

    NASA Astrophysics Data System (ADS)

    Bao, Li-Hong; Zhang, Jiu-Xing; Zhou, Shen-Lin; Wei, Yong-Feng

    2010-10-01

    The grain size controlled bulk Lanthanum hexaboride (LaBe) cathode material was prepared by using the spark plasma sintering method in an oxygen free system. The starting precursor nanopowders with average grain size of 50 nm were prepared by high-energy ball milling. The nanopowder was fully densified at 1300° C, which is about 350° C lower than the sintering temperature of the coarse powders. The thermionic emission current density was measured to be 42.0 A/cm2, which is much higher than 24.2 A/cm2 of coarse powders and Vickers hardness to be 1860 kg/mm2, which is also higher than 1700 kg/mm2 of coarse one. These results indicate that refining the powder grain size to nano level was beneficial for reducing the sintering temperature and promoting the thermionic emission and mechanic properties.

  2. Hydrothermal synthesis of sodium vanadate nanobelts as high-performance cathode materials for lithium batteries

    NASA Astrophysics Data System (ADS)

    Yang, Kaiwen; Fang, Guozhao; Zhou, Jiang; Qin, Mulan; Tang, Yan; Pan, Anqiang; Liang, Shuquan

    2016-09-01

    The sodium vanadate (Na0.76V6O15) nanobelts have been successfully synthesized via a facile hydrothermal reaction followed by annealing. The ultra-long nanobelts have a length ranging from several micrometers to several dozens of micrometers. As cathode materials for lithium-ion batteries, the Na0.76V6O15 nanobelts exhibit high discharge capacity, excellent cyclic stability and good rate capability. High discharge capacity of 248 and 214 mA h g-1 can be obtained at the current density of 300 and 500 mA g-1, respectively. Meanwhile, it maintains a stable capacity of 113 mA h g-1 after 200 cycles at a high current density of 2000 mA g-1 with no capacity decay. The superior electrochemical performances may be attributed to the novel nanobelts structure and excellent structural stability of Na0.76V6O15.

  3. Enhancing the stability of microplasma device utilizing diamond coated carbon nanotubes as cathode materials

    SciTech Connect

    Chang, Tinghsun; Sankaran, Kamatchi Jothiramalingam; Tai, Nyanhwa E-mail: inanlin@mail.tku.edu.tw; Kunuku, Srinivasu; Leou, Keh-Chyang; Lin, I-Nan E-mail: inanlin@mail.tku.edu.tw

    2014-06-02

    This paper reports the enhanced stability of a microplasma device by using hybrid-granular-structured diamond (HiD) film coated carbon nanotubes (CNTs) as cathode, which overcomes the drawback of short life time in the CNTs-based one. The microplasma device can be operated more than 210 min without showing any sign of degradation, whereas the CNTs-based one can last only 50 min. Besides the high robustness against the Ar-ion bombardment, the HiD/CNTs material also possesses superior electron field emission properties with low turn-on field of 3.2 V/μm, which is considered as the prime factor for the improved plasma illumination performance of the devices.

  4. Impact of ALD Coating on Mn-rich Cathode Materials (Presentation)

    SciTech Connect

    Santhanagopalan, S.

    2013-06-01

    LG Chem Power Inc. (LGCPI) and NREL have collaborated to demonstrate the scalability of the atomic layer deposition (ALD) coating process over the last 6 months, and the benefits of ALD coatings for long-term cycling and calendar life are being quantified. The objectives of this work are two-fold: 1) to evaluate the scalability of the process to coat LGCPI cathodes with alumina using the ALD technique, and 2) to demonstrate improvements in rate capability and life of ALD-coated LGCPI electrodes. NREL received samples of baseline material to be coated from LGCPI. NREL carried out ALD coating of the samples with help from a subcontractor, ALD Nanosolutions. NREL fabricated cells from those samples for quick screening and feedback to ALD Nanosolutions. LGCPI is currently fabricating larger-format cells for further evaluation.

  5. Studies on LiFePO 4 as cathode material using impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Schmidt, Jan Philipp; Chrobak, Thorsten; Ender, Moses; Illig, Jörg; Klotz, Dino; Ivers-Tiffée, Ellen

    Lithium iron phosphate is a promising cathode material for the use in hybrid electrical vehicles (HEV) meeting the demands of good stability during cycling and safe operation due to reduced risk of thermal runaway. However, slow solid state diffusion and poor electrical conductivity reduce power capability. For further improvement, the identification of the rate determining processes is necessary. Electrochemical impedance spectroscopy (EIS) has proven to be a powerful tool for the characterization of electrochemical systems. In this contribution a deconvolution of the impedance with the distribution of relaxation times (DRTs) is used to obtain a better resolution in frequency domain. Therewith, the relevant loss processes are identified and an impedance model is developed. Using DRT and CNLS-fit allows the determination of time constants and polarization resistances of all relevant loss processes. Furthermore, their temperature behavior is studied and a physical interpretation is provided.

  6. CO₂ and O₂ evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study.

    PubMed

    Wang, Hongsen; Rus, Eric; Sakuraba, Takahito; Kikuchi, Jun; Kiya, Yasuyuki; Abruña, Héctor D

    2014-07-01

    A three-electrode differential electrochemical mass spectrometry (DEMS) cell has been developed to study the oxidative decomposition of electrolytes at high voltage cathode materials of Li-ion batteries. In this DEMS cell, the working electrode used was the same as the cathode electrode in real Li-ion batteries, i.e., a lithium metal oxide deposited on a porous aluminum foil current collector. A charged LiCoO2 or LiMn2O4 was used as the reference electrode, because of their insensitivity to air, when compared to lithium. A lithium sheet was used as the counter electrode. This DEMS cell closely approaches real Li-ion battery conditions, and thus the results obtained can be readily correlated with reactions occurring in real Li-ion batteries. Using DEMS, the oxidative stability of three electrolytes (1 M LiPF6 in EC/DEC, EC/DMC, and PC) at three cathode materials including LiCoO2, LiMn2O4, and LiNi(0.5)Mn(1.5)O4 were studied. We found that 1 M LiPF6 + EC/DMC electrolyte is quite stable up to 5.0 V, when LiNi(0.5)Mn(1.5)O4 is used as the cathode material. The EC/DMC solvent mixture was found to be the most stable for the three cathode materials, while EC/DEC was the least stable. The oxidative decomposition of the EC/DEC mixture solvent could be readily observed under operating conditions in our cell even at potentials as low as 4.4 V in 1 M LiPF6 + EC/DEC electrolyte on a LiCoO2 cathode, as indicated by CO2 and O2 evolution. The features of this DEMS cell to unveil solvent and electrolyte decomposition pathways are also described.

  7. Novel ruthenium pyrochlore materials for cathode application in intermediate temperature solid oxide fuel cells (IT-SOFCs)

    NASA Astrophysics Data System (ADS)

    Abate, Chiara

    The performance of solid oxide fuel cells, which operate in the temperature range of 500- 700°C (IT-SOFCs), strongly depends on the cathode employed because the interfacial polarization increases rapidly with decreasing temperature. Pyrochlore oxides with Ru on the B-site of the crystal lattice have been shown to have excellent electro catalytic behaviour for oxygen reduction reaction and high electrical conductivity. These characteristics make pyrochlore ruthenates good candidates for IT-SOFCs cathodes. In this work, several compositions of Y2-xPrxRu 2O7 (x = 0, 0.2, 0.5, 1, 1.5, 2) pyrochlore powders were prepared by a soft precipitation method. All the synthesized powders were single pyrochlore phase with particles size depending on the material compositions. Praseodymium (Pr) was introduced in the A-site with the intent to improve the material electrical proprieties and consequently the overall cathode performance. In fact, without destabilizing the pyrochlore structure, Pr caused structural changes that allow higher electron mobility. The electrical measurements showed that the electrical conductivity of the material increased with increasing the Pr content. Compositions of Y2-xPrxRu2O7 were tested as a cathode to compare its electro-catalytic effect with either of two electrolytes, gadolinium doped ceria (GDC) or erbium stabilized bismuth oxide (ESB). Both systems, Y2-xPrxRu2O 7/ESB and Y2-xPrxRu2O7/GDC, showed a similar variation of the electrode area specific resistance (ASR) with Pr content. This trend was shown to be due to a change of the cathode microstructure upon increasing Pr content. The 25 mol % Pr cathode material on ESB electrolyte presented the best performance. A change of ASR as a function of oxygen partial pressure suggested that the oxygen diffusion is the limiting step of the electrode kinetics. Hence, the better cathode performance on ESB resulted from a much lower charge transfer resistance compared to the GDC system. A partial solid

  8. Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

    2016-06-01

    In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

  9. First principle computational and experimental studies of cathode materials for lithium ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Saavedra Arias, Jose Javier

    We have studied the properties of spinel and layered cathode materials for Li ion rechargeable batteries. The analysis was done by first principle calculations, and experimental techniques to elucidate materials that can substitute the presently commercialized material, namely LiCoO 2. We have studied the influence of Ni substitution for Mn in spinel Li 2MnO4. To understand the effects of this substitution on the crystal structure and electronic properties, first principle DFT calculations were performed using VASP. The substitution was done systematically for up to 25% of Mn replacement by Ni in a super cell configuration. Furthermore, the influence of Ni substitution on lithium hoping pathways between the two stable Li positions was also studied by first principle calculations in LiMn 2-xNixO4. These calculations revealed that Ni substitution for Mn in LiMn2O4 indeed improved Li ion mobility. Thereafter, systematic experimental studies were performed on LiMn 2-xNixO4 (0materials were synthesized by solution route and their structural characterization was done using X-ray diffraction (XRD) and Raman spectroscopy. The electrochemical performance of LiMn2-xNi xO4 materials was evaluated in two electrode CR2032 type coin cell configuration with Li metal as anode and liquid electrolyte (1 M LiPF6 in EC:DMC=1:1 v/v). Our results showed significant enhancement in the electrochemical properties with 25% of Ni substitution in LiMn 2O4, which is in good agreement with the theoretical calculations. We also studied layered cathode materials both theoretically and experimentally. The First principle calculations in conjunction with alloy metal method were used to evaluate the average voltage and phase stability of LiMO2 (M=Co, Ni, Mn, W) systems. By formation energy analysis we established that LiNi0.8Co0.1Mn0.1O2 is a promising candidate cathode material. Single

  10. Sodium iron hexacyanoferrate with high Na content as a Na-rich cathode material for Na-ion batteries

    SciTech Connect

    You, Ya; Yu, Xi -Qian; Yin, Ya -Xia; Nam, Kyung -Wan; Guo, Yu -Guo

    2014-10-27

    Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large-scale grids. Increasing the Na content in cathode material is one of the effective ways to achieve high energy density. Prussian blue and its analogues (PBAs) are promising Na-rich cathode materials since they can theoretically store two Na ions per formula. However, increasing the Na content in PBAs cathode materials is a big challenge in the current. Here we show that sodium iron hexacyanoferrate with high Na content could be obtained by simply controlling the reducing agent and reaction atmosphere during synthesis. The Na content can reach as high as 1.63 per formula, which is the highest value for sodium iron hexacyanoferrate. This Na-rich sodium iron hexacyanoferrate demonstrates a high specific capacity of 150 mA h g-1 and remarkable cycling performance with 90% capacity retention after 200 cycles. Furthermore, the Na intercalation/de-intercalation mechanism is systematically studied by in situ Raman, X-ray diffraction and X-ray absorption spectroscopy analysis for the first time. As a result, the Na-rich sodium iron hexacyanoferrate could function as a plenteous Na reservoir and has great potential as a cathode material toward practical Na-ion batteries.

  11. Thianthrene-functionalized polynorbornenes as high-voltage materials for organic cathode-based dual-ion batteries.

    PubMed

    Speer, Martin E; Kolek, Martin; Jassoy, Jean Jacques; Heine, Jennifer; Winter, Martin; Bieker, Peter M; Esser, Birgit

    2015-10-25

    Thianthrene-functionalized polynorbornenes were investigated as high-voltage organic cathode materials for dual-ion cells. The polymers show reversible oxidation reactions in solution and as a solid in composite electrodes. Constant current investigations displayed a capacity of up to 66 mA h g(-1) at a high potential of 4.1 V vs. Li/Li(+).

  12. Thianthrene-functionalized polynorbornenes as high-voltage materials for organic cathode-based dual-ion batteries.

    PubMed

    Speer, Martin E; Kolek, Martin; Jassoy, Jean Jacques; Heine, Jennifer; Winter, Martin; Bieker, Peter M; Esser, Birgit

    2015-10-25

    Thianthrene-functionalized polynorbornenes were investigated as high-voltage organic cathode materials for dual-ion cells. The polymers show reversible oxidation reactions in solution and as a solid in composite electrodes. Constant current investigations displayed a capacity of up to 66 mA h g(-1) at a high potential of 4.1 V vs. Li/Li(+). PMID:26235336

  13. Sodium iron hexacyanoferrate with high Na content as a Na-rich cathode material for Na-ion batteries

    DOE PAGES

    You, Ya; Yu, Xi -Qian; Yin, Ya -Xia; Nam, Kyung -Wan; Guo, Yu -Guo

    2014-10-27

    Owing to the worldwide abundance and low-cost of Na, room-temperature Na-ion batteries are emerging as attractive energy storage systems for large-scale grids. Increasing the Na content in cathode material is one of the effective ways to achieve high energy density. Prussian blue and its analogues (PBAs) are promising Na-rich cathode materials since they can theoretically store two Na ions per formula. However, increasing the Na content in PBAs cathode materials is a big challenge in the current. Here we show that sodium iron hexacyanoferrate with high Na content could be obtained by simply controlling the reducing agent and reaction atmospheremore » during synthesis. The Na content can reach as high as 1.63 per formula, which is the highest value for sodium iron hexacyanoferrate. This Na-rich sodium iron hexacyanoferrate demonstrates a high specific capacity of 150 mA h g-1 and remarkable cycling performance with 90% capacity retention after 200 cycles. Furthermore, the Na intercalation/de-intercalation mechanism is systematically studied by in situ Raman, X-ray diffraction and X-ray absorption spectroscopy analysis for the first time. As a result, the Na-rich sodium iron hexacyanoferrate could function as a plenteous Na reservoir and has great potential as a cathode material toward practical Na-ion batteries.« less

  14. Template-assisted formation of porous vanadium oxide as high performance cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Su, Yanhui; Pan, Anqiang; Wang, Yaping; Huang, Jiwu; Nie, Zhiwei; An, Xinxin; Liang, Shuquan

    2015-11-01

    Similar to carbonaceous materials, porous metal oxides have attracted wide attention in energy storage and conversion systems because of their structural advantages, including high activity and electrolyte accessibility. In this work, we report the novel preparation of porous vanadium pentoxide (V2O5) as high performance cathode material for lithium ion batteries. Ketjen black (KB), a porous carbon material, has been employed as hard templates to host precursor species in their porous structures. The porous V2O5 electrode material is prepared after removing the KB carbon framework by calcinating the composites in air. As cathode materials for lithium ion batteries, the porous V2O5 electrodes exhibit high capacity, good cycling stability and rate capability. An initial discharge capacity of 141.1 mA h g-1 is delivered at a current density of 100 mAg-1, very close to the theoretical capacity of 147 mA h g-1.

  15. Investigating the stability of cathode materials for rechargeable lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Huang, Yiqing

    Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P

  16. Strontium-doped samarium manganite as cathode materials for oxygen reduction reaction in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Li, W.; Xiong, C. Y.; Jia, L. C.; Pu, J.; Chi, B.; Chen, X.; Schwank, J. W.; Li, J.

    2015-06-01

    SmxSr1-xMnO3 with x = 0.3, 0.5 and 0.8, denoted as SSM37, SSM55 and SSM82, respectively, have been prepared via a sol-gel route as materials for cathodes in solid oxide fuel cells. Their activities in the oxygen reduction reaction (ORR) have been evaluated in comparison with the state-of-the-art cathode material La0.8Sr0.2MnO3 (LSM82) by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). Among all the prepared cathodes, the SSM55 exhibits the lowest values, while the LSM82 exhibits the highest polarization resistance, at open circuit voltage (OCV) and temperatures from 650 to 800 °C. This result indicates that the prepared SmxSr1-xMnO3 is a promising replacement for LSM82 as cathode material for SOFCs, and the SSM55 represents the optimal concentration in SmxSr1-xMnO3 series. The remarkably high ORR activity of the SSM55 is ascribed to its high surface Mn4+/Mn3+ and Oad/Olattice ratios and fast surface oxygen exchange kinetics.

  17. Sintered wire cathode

    DOEpatents

    Falce, Louis R.; Ives, R. Lawrence

    2009-06-09

    A porous cathode structure is fabricated from a plurality of wires which are placed in proximity to each other in elevated temperature and pressure for a sintering time. The sintering process produces the porous cathode structure which may be divided into a plurality of individual porous cathodes, one of which may be placed into a dispenser cathode support which includes a cavity for containing a work function reduction material such as BaO, CaO, and Al.sub.2O.sub.3. The work function reduction material migrates through the pores of the porous cathode from a work replenishment surface adjacent to the cavity of the dispenser cathode support to an emitting cathode surface, thereby providing a dispenser cathode which has a uniform work function and therefore a uniform electron emission.

  18. Depression cathode structure for cathode ray tubes having surface smoothness and method for producing same

    SciTech Connect

    Rychlewski, T.V.

    1984-10-23

    Depression cathode structures for cathode ray tubes are produced by dispensing liquid cathode material into the depression of a metallic supporting substrate, removing excess cathode material by passing a doctor blade across the substrate surface and over the depression, and drying the cathode layer to a substantially immobile state. The cathode layer may optionally be further shaped prior to substantially complete drying thereof.

  19. Facet Dependent Disorder in the Pristine High Voltage Lithium-Manganese-Rich Cathode Material

    SciTech Connect

    Dixit, Hemant M.; Zhou, Wu; Idrobo Tapia, Juan Carlos; Nanda, Jagjit; Cooper, Valentino R.

    2014-11-21

    Defects and surface reconstructions are thought to be crucial for the long term stability of high-voltage lithium-manganese-rich cathodes. Unfortunately, many of these defects arise only after electrochemical cycling which occur under harsh conditions making it difficult to fully comprehend the role they play in degrading material performance. Recently, it has been observed that defects are present even in the pristine material. This study, therefore, focuses on examining the nature of the disorder observed in pristine Li$_{1.2}$Ni$_{0.175}$Mn$_{0.525}$Co$_{0.1}$O$_2$ (LNMCO) particles. Using atomic resolution Z-contrast imaging and electron energy-loss spectroscopy measurements we show that there are indeed a significant amount of anti-site defects present in this material; with transition metals substituting on Li metal sites. Furthermore, we find a strong tendency of segregation of these types of defects towards open facets (surfaces perpendicular to the layered arrangement of atoms), rather than closed facets (surfaces parallel to the layered arrangement of atoms). First principles calculations identify anti-site defect pairs of Ni swapping with Li ions as the predominant defect in the material. Furthermore, energetically favorable swapping of Ni on the Mn sites were observed to lead to Mn depletion at open facets. Relatively, low Ni migration barriers also support the notion that Ni are the predominant cause of disorder. These insights suggests that certain facets of the LNMCO particles may be more useful for inhibiting surface reconstruction and improving the stability of these materials through careful consideration of the exposed surface.

  20. Facet Dependent Disorder in the Pristine High Voltage Lithium-Manganese-Rich Cathode Material

    DOE PAGES

    Dixit, Hemant M.; Zhou, Wu; Idrobo Tapia, Juan Carlos; Nanda, Jagjit; Cooper, Valentino R.

    2014-11-21

    Defects and surface reconstructions are thought to be crucial for the long term stability of high-voltage lithium-manganese-rich cathodes. Unfortunately, many of these defects arise only after electrochemical cycling which occur under harsh conditions making it difficult to fully comprehend the role they play in degrading material performance. Recently, it has been observed that defects are present even in the pristine material. This study, therefore, focuses on examining the nature of the disorder observed in pristine Limore » $$_{1.2}$$Ni$$_{0.175}$$Mn$$_{0.525}$$Co$$_{0.1}$$O$_2$ (LNMCO) particles. Using atomic resolution Z-contrast imaging and electron energy-loss spectroscopy measurements we show that there are indeed a significant amount of anti-site defects present in this material; with transition metals substituting on Li metal sites. Furthermore, we find a strong tendency of segregation of these types of defects towards open facets (surfaces perpendicular to the layered arrangement of atoms), rather than closed facets (surfaces parallel to the layered arrangement of atoms). First principles calculations identify anti-site defect pairs of Ni swapping with Li ions as the predominant defect in the material. Furthermore, energetically favorable swapping of Ni on the Mn sites were observed to lead to Mn depletion at open facets. Relatively, low Ni migration barriers also support the notion that Ni are the predominant cause of disorder. These insights suggests that certain facets of the LNMCO particles may be more useful for inhibiting surface reconstruction and improving the stability of these materials through careful consideration of the exposed surface.« less

  1. Facet-dependent disorder in pristine high-voltage lithium-manganese-rich cathode material.

    PubMed

    Dixit, Hemant; Zhou, Wu; Idrobo, Juan-Carlos; Nanda, Jagjit; Cooper, Valentino R

    2014-12-23

    Defects and surface reconstructions are thought to be crucial for the long-term stability of high-voltage lithium-manganese-rich cathodes. Unfortunately, many of these defects arise only after electrochemical cycling which occurs under harsh conditions, making it difficult to fully comprehend the role they play in degrading material performance. Recently, it has been observed that defects are present even in the pristine material. This study, therefore, focuses on examining the nature of the disorder observed in pristine Li1.2Ni0.175Mn0.525Co0.1O2 (LNMCO) particles. Using atomic-resolution Z-contrast imaging and electron energy loss spectroscopy measurements, we show that there is indeed a significant amount of antisite defects present in this material, with transition metals substituting on Li metal sites. Furthermore, we find a strong segregation tendency of these types of defects toward open facets (surfaces perpendicular to the layered arrangement of atoms) rather than closed facets (surfaces parallel to the layered arrangement of atoms). First-principles calculations identify antisite defect pairs of Ni swapping with Li ions as the predominant defect in the material. Furthermore, energetically favorable swapping of Ni on the Mn sites was observed to lead to Mn depletion at open facets. Relatively, low Ni migration barriers also support the notion that Ni is the predominant cause of disorder. These insights suggest that certain facets of the LNMCO particles may be more useful for inhibiting surface reconstruction and improving the stability of these materials through careful consideration of the exposed surface.

  2. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries.

    PubMed

    Lin, Feng; Markus, Isaac M; Nordlund, Dennis; Weng, Tsu-Chien; Asta, Mark D; Xin, Huolin L; Doeff, Marca M

    2014-03-27

    The present study sheds light on the long-standing challenges associated with high-voltage operation of LiNi(x)Mn(x)Co(1-2x)O2 cathode materials for lithium-ion batteries. Using correlated ensemble-averaged high-throughput X-ray absorption spectroscopy and spatially resolved electron microscopy and spectroscopy, here we report structural reconstruction (formation of a surface reduced layer, to transition) and chemical evolution (formation of a surface reaction layer) at the surface of LiNi(x)Mn(x)Co(1-2x)O2 particles. These are primarily responsible for the prevailing capacity fading and impedance buildup under high-voltage cycling conditions, as well as the first-cycle coulombic inefficiency. It was found that the surface reconstruction exhibits a strong anisotropic characteristic, which predominantly occurs along lithium diffusion channels. Furthermore, the surface reaction layer is composed of lithium fluoride embedded in a complex organic matrix. This work sets a refined example for the study of surface reconstruction and chemical evolution in battery materials using combined diagnostic tools at complementary length scales.

  3. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lin, Feng; Markus, Isaac M.; Nordlund, Dennis; Weng, Tsu-Chien; Asta, Mark D.; Xin, Huolin L.; Doeff, Marca M.

    2014-03-01

    The present study sheds light on the long-standing challenges associated with high-voltage operation of LiNixMnxCo1-2xO2 cathode materials for lithium-ion batteries. Using correlated ensemble-averaged high-throughput X-ray absorption spectroscopy and spatially resolved electron microscopy and spectroscopy, here we report structural reconstruction (formation of a surface reduced layer, to transition) and chemical evolution (formation of a surface reaction layer) at the surface of LiNixMnxCo1-2xO2 particles. These are primarily responsible for the prevailing capacity fading and impedance buildup under high-voltage cycling conditions, as well as the first-cycle coulombic inefficiency. It was found that the surface reconstruction exhibits a strong anisotropic characteristic, which predominantly occurs along lithium diffusion channels. Furthermore, the surface reaction layer is composed of lithium fluoride embedded in a complex organic matrix. This work sets a refined example for the study of surface reconstruction and chemical evolution in battery materials using combined diagnostic tools at complementary length scales.

  4. Monolithic cathodes

    NASA Astrophysics Data System (ADS)

    Davis, P. R.; Swanson, L. W.

    1985-11-01

    The purpose of this program was to evaluate LaB6 (210) and (310) oriented single crystal material for flat cathode applications and to deliver mounted LaB6 cathodes with (310) orientation for operation in RADC/Varian life test vehicles. To that end, the program was divided into four separate tasks, as shown in the report. This project was extended for 3 months past the initial program period so that unavoidable delays could be overcome and the project completed. The final report covers the entire period of the program, which terminated 29 March 1985.

  5. Electrochemical Effects of Atomic Layer Deposition on Cathode Materials for Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Scott, Isaac David

    One of the greatest challenges of modern society is to stabilize a consistent energy supply that will meet our growing energy demand while decreasing the use of fossil fuels and the harmful green house gases which they produce. Developing reliable and safe solutions has driven research into exploring alternative energy sources for transportation including fuel cells, hydrogen storage, and lithium-ion batteries (LIBs). For the foreseeable future, though, rechargeable batteries appear to be the most practically viable power source. To deploy LIBs in next-generation vehicles, it is essential to develop electrodes with durability, high energy density, and high power. Unfortunately, the power capability of LIBs is generally hindered by Li+-ion diffusion in micrometer-sized materials and the formation of an insulating solid electrolyte interface (SEI) layer on the surface of the active material. In addition, degradation of the battery material due to chemical and electrochemical reactions with the electrolyte lead to both capacity fade and safety concerns both at room and higher temperatures. The current study focuses on mitigating these issues for high voltage cathode materials by both using nanoscale particles to improve Li+-ion diffusion and using ultrathin nanoscale coatings to protect the battery materials from undesirable side reactions. The electrode material is coated with Al2O3 using atomic layer deposition (ALD), which is a method to grow conformal thin films with atomic thickness (angstrom level control) using sequential, self-limiting surface reactions. First, nano-LiCoO 2 is employed to demonstrate the effectiveness of ALD coatings and demonstrates a profound increase in rate performance (>250% improvement) over generally employed micrometer-sized particles. Second, the cathode materials LiNi 0.8Co0.15Al0.05O2, LiNi0.33Mn 0.33Co0.33O2, LiMn2O4, and LiNi0.5Mn1.5O4 were used to demonstrate the benefits ALD coatings have on thermal runaway. The results show a

  6. Structure of electrolyte decomposition products on high voltage spinel cathode materials determined by in situ neutron reflectometry

    NASA Astrophysics Data System (ADS)

    Browning, Jim; Veith, Gabriel; Baggetto, Loic; Dudney, Nancy; Tenhaeff, Wyatt

    2012-02-01

    Interfacial reactions on electrical energy storage (EES) materials mediate their stability, durability, and cycleablity. Understanding these reactions in situ is difficult since they occur at the liquid-solid interface of an optically absorbing material that hinders the use of techniques such as infra-red spectroscopy. Furthermore, since the interfaces involve liquids classic vacuum-based analytical methods can only probe reaction products, which are stable under vacuum. Here, we present the results of an in situ neutron reflectometry study detailing the formation of a thick solid-electrolyte interphase (SEI) on a high voltage spinel cathode material. The cathode/electrolyte system used in this study is a LiMn1.5Ni0.5O4 thin film subjected to a 1.2 molar LiPF6 in 1:1 ethylene carbonate - dimethyl carbonate electrolyte solution.

  7. Excellent cycling stability and superior rate capability of a graphene-amorphous FePO4 porous nanowire hybrid as a cathode material for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Gaoliang; Ding, Bing; Wang, Jie; Nie, Ping; Dou, Hui; Zhang, Xiaogang

    2016-04-01

    A porous nanowire material consisting of graphene-amorphous FePO4 was investigated as an advanced cathode material for sodium ion batteries for large-scale applications. This hybrid cathode material showed excellent cycling performance and superior rate capability, which were attributed to the porous nanowire structure and the existence of graphene.A porous nanowire material consisting of graphene-amorphous FePO4 was investigated as an advanced cathode material for sodium ion batteries for large-scale applications. This hybrid cathode material showed excellent cycling performance and superior rate capability, which were attributed to the porous nanowire structure and the existence of graphene. Electronic supplementary information (ESI) available: Experimental section; SEM images, BET, XPS spectrum, TG curve and EIS spectra of the samples; the comparison of electrochemical performance with the reported results. See DOI: 10.1039/c6nr00409a

  8. Li2S-reduced graphene oxide nanocomposites as cathode material for lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Han, Kai; Shen, Jingmei; Hayner, Cary M.; Ye, Hongqi; Kung, Mayfair C.; Kung, Harold H.

    2014-04-01

    A lithium sulfide-reduced graphene oxide nanocomposite (Li2S-rGO) was synthesized and evaluated as the cathode material and Li source for the assembly of Li-S batteries. The composite, with a unique 3-D pocket structure, was synthesized by a combination of facile solution chemistry and thermal treatment. The as-prepared Li2S-rGO nanocomposites were characterized by X-ray photoelectron spectroscopy, X-ray diffraction and scanning electron microscopy, which showed 20-40 nm Li2S particles homogeneously dispersed between reduced graphene oxide sheets. Li2S contents as high as ∼66% could be obtained. When used with an electrolyte containing LiNO3 and polysulfide, the Li2S-rGO nanocomposites exhibited a high initial capacity of 982 mAh g-1 Li2S. However, there was noticeable capacity fade in subsequent cycles, probably due to polysulfide dissolution and the shuttle mechanism, but a capacity of 315 mAh g-1 could still be obtained after 100 cycles, with 90-95% coulomb efficiency. The effect of polysulfide additive in the electrolyte on the activation of Li2S in the first delithiation step was discussed.

  9. Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

    SciTech Connect

    Ratnakumar, B.V.; Ni, C.L.; DiStefano, S.; Nagasubramanian, G.; Bankston, C.P.

    1989-01-01

    Niobium triselenide offers promise as a high energy density cathode material for ambient temperature lithium rechargeable cells. The electrochemical behavior of NbSe/sub 3/ in the battery electrolyte, i.e., 1.5m LiAsF/sub 6//2 Me-THF is reported here. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe/sub 3/ as well as the rate governing processes in the reduction of NbSe/sub 3/. Based on the experimental data, an equivalent circuit has been formulated to represent the NbSe/sub 3/-solution interface. The kinetic parameters for the reduction of NbSe/sub 3/ were evaluated from the ac and dc measurements. Finally, the structural change in NbSe/sub 3/ on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe/sub 3/ was identified to be a loss of crystallographic order, i.e., amorphous by x-ray diffraction.

  10. Binary and ternary nano-catalysts as cathode materials in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Trimm, Bryan Dunning

    The need for alternative energy, in order to reduce dependence on petroleum based fuels, has increased in recent years. Public demand is at an all-time high for low emitting or none polluting energy sources, driving the research for cleaner technology. Lithium batteries and fuel cells have the ability to produce this alternative energy with much cleaner standards, while allowing for portability and high energy densities. This work focuses on the performance of nanocatalysts in Proton Exchange Membrane Fuel Cell or PEMFC. A key technical challenge is the sluggish rate for oxygen reduction reaction at the cathode of PEMFC, which requires highly-active and stable catalysts. Our investigation is directed at increasing stability and durability as well as reducing high loading of noble metals in these catalyst materials. Binary and ternary structured nanomaterials, e.g., Pt51V1Co48/C and Pd xCu1-x/C, have been synthesized and tested in a PEMFC, in order to gain a better understanding of their durability and efficiency. In addition to electrochemical characterization, synchrotron x-ray techniques at the Advance Photon Source in Argonne National Lab have also been used for the structural characterization.

  11. Reduced graphene oxide enwrapped vanadium pentoxide nanorods as cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Dezhi; Quan, Hongying; Luo, Shenglian; Luo, Xubiao; Deng, Fang; Jiang, Hualin

    2014-02-01

    Novel reduced graphene oxide/vanadium pentoxide (rGO/V2O5) nanocomposites were fabricated by coassembly between negatively charged graphene oxide and positively charged oxide nanorods. A series of characterization including X-ray diffraction, Raman spectrum, scanning electron microscopy and transmission electron microscopy indicated that the V2O5 nanorods with the width of about 50 nm and the length from a few hundred nanometers to several micrometers were enwrapped by rGO layers to form core-shell nanostructures. Compared with the pristine V2O5 nanorods, the as-prepared rGO/V2O5 nanocomposites with 13 wt% rGO showed a significantly enhanced electrochemical performance with high reversible capacities, good cycling stabilities and excellent rate capabilities as a cathode material for lithium batteries. The rGO/V2O5 nanocomposites electrodes delivered a stable discharge capacity around 140 mA h g-1 at a current density of 150 mA g-1 for 100 cycles in the voltage range of 2.5-4.0 V. Furthermore, the nanocomposites electrodes delivered discharge capacities of 287 mA h g-1 and 207 mA h g-1 during the first and 50th cycles in the voltage range of 2.0-4.0 V at a current density of 100 mA g-1, respectively. The as-synthesized nanocomposites are promising candidates for electrical energy storage applications.

  12. Surface modified CFx cathode material for ultrafast discharge and high energy density

    SciTech Connect

    Dai, Yang; Zhu, Yimei; Cai, Sendan; Wu, Lijun; Yang, Weijing; Xie, Jingying; Wen, Wen; Zheng, Jin-Cheng; Zheng, Yi

    2014-11-10

    Li/CFx primary possesses the highest energy density of 2180 W h kg⁻¹ among all primary lithium batteries. However, a key limitation for the utility of this type of battery is in its poor rate capability because the cathode material, CFx, is an intrinsically poor electronic conductor. Here, we report on our development of a controlled process of surface de-fluorination under mild hydrothermal conditions to modify the highly fluorinated CFx. The modified CFx, consisting of an in situ generated shell component of F-graphene layers, possesses good electronic conductivity and removes the transporting barrier for lithium ions, yielding a high-capacity performance and an excellent rate-capability. Indeed, a capacity of 500 mA h g⁻¹ and a maximum power density of 44 800 W kg⁻¹ can be realized at the ultrafast rate of 30 C (24 A g⁻¹), which is over one order of magnitude higher than that of the state-of-the-art primary lithium-ion batteries.

  13. Improvement of Electrochemical Properties of Ni-Rich Cathode Material by Polypyrrole Coating.

    PubMed

    Yoo, Gi-Won; Jang, Byung-Chan; Min, Song-Gi; Son, Jong-Tae

    2016-03-01

    In this study, we attempted a nanosized coating layer of commercial polypyrrole (PPy) on LiNi0.6Co0.1Mn0.3O2 (HNCM) cathode material to overcome the side reactions with electrolyte and a decrease in the capacity of the inert coating layer. The coating method using commercial PPy is very simple. The energy dispersive X-ray spectroscopy (EDS) analysis and transmission electron microscopy (TEM) images confirmed that PPy coating layer was well dispersed and nanosized. The alternating current (AC) impedance studies revealed that the coating of PPy significantly decreased the charge-transfer resistance of HNCM electrodes. Moreover, the 1 wt% PPy-HNCM electrode exhibited good electrochemical performance with a specific discharge capacity of 177.52 mA h g(-1) at a rate of 0.1 C in the voltage range 3.0-4.3 V, whereas the capacity of the HNCM electrode was only 167.13 mA h g(-1). PMID:27455681

  14. Defect physics vis-à-vis electrochemical performance in layered mixed-metal oxide cathode materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang; Johannes, Michelle

    Layered mixed-metal oxides with different compositions of (Ni,Co,Mn) [NCM] or (Ni,Co,Al) [NCA] have been used in commercial lithium-ion batteries. Yet their defect physics and chemistry is still not well understood, despite having important implications for the electrochemical performance. In this presentation, we report a hybrid density functional study of intrinsic point defects in the compositions LiNi1/3Co1/3Mn1/3O2 (NCM1/3) and LiNi1/3Co1/3Al1/3O2 (NCA1/3) which can also be regarded as model compounds for NCM and NCA. We will discuss defect landscapes in NCM1/3 and NCA1/3 under relevant synthesis conditions with a focus on the formation of metal antisite defects and its implications on the electrochemical properties and ultimately the design of NCM and NCA cathode materials.

  15. Re-heating effect of Ni-rich cathode material on structure and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Jo, Jae Hyeon; Jo, Chang-Heum; Yashiro, Hitoshi; Kim, Sun-Jae; Myung, Seung-Taek

    2016-05-01

    The re-heating effect for Ni-rich Li[Ni0.7Mn0.3]O2 is investigated because the process is required in surface modification and removal of adhered water molecules. A representative binary Ni-rich Li[Ni0.7Mn0.3]O2 (in which cationic distribution in Li layers is not affected by heteroelements) is selected and synthesized via co-precipitation. The as-synthesized Ni-rich Li[Ni0.7Mn0.3]O2 is re-heated at 200 °C, 400 °C, and 600 °C, so that the resulting structural and electrochemical properties are compared by means of X-ray diffraction, transmission electron microscopy, time of flight-secondary ion spectroscopy, thermogravimetric analysis, high temperature X-ray diffraction, and electrochemical tests. Raising the re-heating temperature increases the occupancy of Ni2+ in Li layers and accelerates the aggregation of lithium-related compounds such as Li2CO3 and LiOH towards the particle surface. Among the several conditions tested, re-heating at 200 °C results in a negligible change in the crystal structure; specifically, Ni2+ occupation in Li layers, higher capacity with good reversibility upon cycling tests, better rate capability, and thermal properties. Therefore, re-heating of cathode active materials, in particular Ni-rich compositions, should be considered to stabilize both electrode performances and thermal properties.

  16. Crystal and electronic structures of nitridophosphate compounds as cathode materials for Na-ion batteries

    NASA Astrophysics Data System (ADS)

    Debbichi, M.; Lebègue, S.

    2015-08-01

    Using density-functional theory, we have studied the electronic and magnetic properties of two promising compounds that can be used as cathode materials, namely, Na2Fe2P3O9N and Na3TiP3O9N . When Na is extracted, we found the volume change to be quite small, with values of ˜-0.6 % for Na3TiP3O9N and -5 % for Na2Fe2P3O9N . Our calculated voltages with the Hubbard-type correction (GGA+U) approximation are 2.93 V for Na3TiP3O9N /Na2TiP3O9N and 2.68 V for Na2Fe2P3O9N /NaFe2P3O9N , in good agreement with the experimental data. Our results confirm that these compounds are very promising for rechargeable Na-ion batteries.

  17. Improving the electrochemical performance of lithium vanadium fluorophosphate cathode material: Focus on interfacial stability

    NASA Astrophysics Data System (ADS)

    Wang, Jiexi; Liu, Zhaomeng; Yan, Guochun; Li, Hangkong; Peng, Wenjie; Li, Xinhai; Song, Liubin; Shih, Kaimin

    2016-10-01

    To improve the stability of LiVPO4F electrode/electrolyte interface, Li3PO4 is used to modify LiVPO4F composite (P-LVPF) for the first time. Morphological characterization shows that LiVPO4F particles are wrapped by amorphous carbon and lithium ionic conductor Li3PO4 as the interlayer and outer layer, respectively. Compared to the pristine sample, the resultant P-LVPF exhibits greatly improved rate capability and elevated-temperature cycle performance when applied as the cathode material for lithium ion batteries. Specifically, the Li3PO4 modified sample specific capacity maintains 77.6% at 1 C after 100 cycles under 55 °C. Such improvement is attributed to the fact that the Li3PO4 coating layer not only acts as a good ionic conductor for LiVPO4F, but also serves as a physical barrier between electrode and electrolyte which can build a stable interface.

  18. Surface modified CFx cathode material for ultrafast discharge and high energy density

    DOE PAGES

    Dai, Yang; Zhu, Yimei; Cai, Sendan; Wu, Lijun; Yang, Weijing; Xie, Jingying; Wen, Wen; Zheng, Jin-Cheng; Zheng, Yi

    2014-11-10

    Li/CFx primary possesses the highest energy density of 2180 W h kg⁻¹ among all primary lithium batteries. However, a key limitation for the utility of this type of battery is in its poor rate capability because the cathode material, CFx, is an intrinsically poor electronic conductor. Here, we report on our development of a controlled process of surface de-fluorination under mild hydrothermal conditions to modify the highly fluorinated CFx. The modified CFx, consisting of an in situ generated shell component of F-graphene layers, possesses good electronic conductivity and removes the transporting barrier for lithium ions, yielding a high-capacity performance andmore » an excellent rate-capability. Indeed, a capacity of 500 mA h g⁻¹ and a maximum power density of 44 800 W kg⁻¹ can be realized at the ultrafast rate of 30 C (24 A g⁻¹), which is over one order of magnitude higher than that of the state-of-the-art primary lithium-ion batteries.« less

  19. Electronic structure of lithium borocarbide as a cathode material for a rechargeable Li-ion battery: First-principles calculation

    NASA Astrophysics Data System (ADS)

    Xu, Qiang; Ban, Chunmei; Dillon, Anne; Wei, Suhuai; Zhao, Yufeng

    2011-03-01

    Traditional cathode materials, such as transition-metal oxides, are heavy, expensive, and often not benign. Therefore, alternative materials without transition metal elements are highly desirable in order to design high-capacity Li-ion batteries of light weight and low price. Here we report on potential application of the LiBC compound as cathode materials, in which graphene-like BC sheets are intercalated by Li ions. The crystal structure and properties of LiBC were firstly reported by Wörle et al. in 1995. Importantly, it was found that the 75% Li ions can be retrieved out of the compound without changing the layered structure. We have performed first-principles calculations based on density functional theory, as implemented in the Vienna Ab-initio Simulation Package. According to our calculation, the layered Li x BC structure can be well preserved at x > 0.5 . Thereversibleelectrochemicalreaction , LiBC <--> Li 0.5 , gives an energy capacity of 609mAh/g and an open-circuit voltage of 2.42V. The volume change is only about 5% during the charging and discharging process. All these results point to a potentially promising application of LiBC as a novel cathode material for high-capacity Li-ion batteries in replacement of the transition metal oxides.

  20. A Ternary Polyaniline/Active Carbon/Lithium Iron Phosphate Composite as Cathode Material for Lithium Ion Battery.

    PubMed

    Wang, Xiaohong; Zhang, Wuxing; Huang, Yunhui; Xia, Tian; Lian, Yongfu

    2016-06-01

    Lithium iron phosphate (LiFePO4) has been evaluated as the most promising cathode material for the next generation lithium-ion batteries because of its high operating voltage, good cycle performance, low cost, and environmentally friendly safety. However, pure LiFePO4 shows poor reversible capacity and charge/discharge performance at high current density. Many methods including optimization of particle size, introduction of coating carbon and conductive polymer, and the doping of metal and halogen ions have been developed to improve its electrochemical performance. In this study, conductive polymer polyaniline (PANI), active carbon and LiFePO4 (C-LFP/PANI) composite cathodes were successfully prepared by chemical oxidation method. Electrochemical performance shows that a remarkable improvement in capacity and rate performance can be achieved in the C-LFP/PANI composite cathodes with an addition of HCI. In comparison with C-LFP cathode, the C-LFP/PANI doped with HCl composite exhibits ca. 15% and 26% capacity enhancement at 0.2 C and 10 C, respectively. PMID:27427742

  1. A Ternary Polyaniline/Active Carbon/Lithium Iron Phosphate Composite as Cathode Material for Lithium Ion Battery.

    PubMed

    Wang, Xiaohong; Zhang, Wuxing; Huang, Yunhui; Xia, Tian; Lian, Yongfu

    2016-06-01

    Lithium iron phosphate (LiFePO4) has been evaluated as the most promising cathode material for the next generation lithium-ion batteries because of its high operating voltage, good cycle performance, low cost, and environmentally friendly safety. However, pure LiFePO4 shows poor reversible capacity and charge/discharge performance at high current density. Many methods including optimization of particle size, introduction of coating carbon and conductive polymer, and the doping of metal and halogen ions have been developed to improve its electrochemical performance. In this study, conductive polymer polyaniline (PANI), active carbon and LiFePO4 (C-LFP/PANI) composite cathodes were successfully prepared by chemical oxidation method. Electrochemical performance shows that a remarkable improvement in capacity and rate performance can be achieved in the C-LFP/PANI composite cathodes with an addition of HCI. In comparison with C-LFP cathode, the C-LFP/PANI doped with HCl composite exhibits ca. 15% and 26% capacity enhancement at 0.2 C and 10 C, respectively.

  2. Evaluation of Ca3Co2O6 as cathode material for high-performance solid-oxide fuel cell

    PubMed Central

    Wei, Tao; Huang, Yun-Hui; Zeng, Rui; Yuan, Li-Xia; Hu, Xian-Luo; Zhang, Wu-Xing; Jiang, Long; Yang, Jun-You; Zhang, Zhao-Liang

    2013-01-01

    A cobalt-based thermoelectric compound Ca3Co2O6 (CCO) has been developed as new cathode material with superior performance for intermediate-temperature (IT) solid-oxide fuel cell (SOFC). Systematic evaluation has been carried out. Measurement of thermal expansion coefficient (TEC), thermal-stress (σ) and interfacial shearing stress (τ) with the electrolyte show that CCO matches well with several commonly-used IT electrolytes. Maximum power density as high as 1.47 W cm−2 is attained at 800°C, and an additional thermoelectric voltage of 11.7 mV is detected. The superior electrochemical performance, thermoelectric effect, and comparable thermal and mechanical behaviors with the electrolytes make CCO to be a promising cathode material for SOFC. PMID:23350032

  3. Optimization of a microbial fuel cell for wastewater treatment using recycled scrap metals as a cost-effective cathode material.

    PubMed

    Lefebvre, Olivier; Tan, Zi; Shen, Yujia; Ng, How Y

    2013-01-01

    Microbial fuel cell (MFC) for wastewater treatment is still hindered by the prohibitive cost of cathode material, especially when platinum is used to catalyze oxygen reduction. In this study, recycled scrap metals could be used efficiently as cathode material in a specially-designed MFC. In terms of raw power, the scrap metals ranked as follows: W/Co > Cu/Ni > Inconel 718 > carpenter alloy; however, in terms of cost and long term stability, Inconel 718 was the preferred choice. Treatment performance--assessed on real and synthetic wastewater--was considerably improved either by filling the anode compartment with carbon granules or by operating the MFC in full-loop mode. The latter option allowed reaching 99.7% acetate removal while generating a maximum power of 36 W m(-3) at an acetate concentration of 2535 mg L(-1). Under these conditions, the energy produced by the system averaged 0.1 kWh m(-3) of wastewater treated.

  4. Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries.

    PubMed

    Huang, Yiqing; Lin, Yuh-Chieh; Jenkins, David M; Chernova, Natasha A; Chung, Youngmin; Radhakrishnan, Balachandran; Chu, Iek-Heng; Fang, Jin; Wang, Qi; Omenya, Fredrick; Ong, Shyue Ping; Whittingham, M Stanley

    2016-03-23

    The thermal stability of electrochemically delithiated Li0.1Ni0.8Co0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4, and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability of the delithiated materials is found to be in the order of NCA < VOPO4 < MFP < FP. Unlike the layered oxides and MFP, VOPO4 does not evolve O2 on heating. Thus, VOPO4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO4, Li2VOPO4, and LiNi0.8Co0.15Al0.05O2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absence of electrolyte. An analysis of the reaction equilibria between VOPO4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results.

  5. Hard X-ray Fluorescence Measurements of Heteroepitaxial Solid Oxide Fuel Cell Cathode Materials

    SciTech Connect

    Davis, Jacob N.; Miara, Lincoln J.; Saraf, Laxmikant V.; Kaspar, Tiffany C.; Gopalan, Srikanth; Pal, Uday B.; Woicik, Joseph C.; Basu, Soumendra N.; Ludwig, Karl F.

    2012-12-01

    Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the surface chemical states of cations in the surface of the SOFC cathode is vital to designing a system that will perform well at lower temperatures. The samples studied were grown by pulsed laser deposition (PLD) at the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). 20% strontium doped lanthanum manganite (LSM-20) was grown on YSZ and NGO (neodymium gallate). The films on YSZ have a fiber texture. LSM-20 on NGO is heteroepitaxial. Lanthanum strontium cobalt ferrite (LSCF-6428) films were grown on LAO and YSZ with a GDC barrier layer. Total X-ray Reflection Fluorescence (TXRF) was used to depth profile the samples. In a typical experiment, the angle of the incident beam is varied though the critical angle. Below the critical angle, the x-ray decays as an evanescent wave and will only penetrate the top few nanometers. TXRF experiments done on LSM films have suggested strontium segregates to the surface and form strontium enriched nanoparticles (1). It should be pointed out that past studies have focused on 30% strontium A-site doping, but this project uses 20% strontium doped lanthanum manganite. XANES and EXAFS data were taken as a function of incoming angle to probe composition as a function of depth. XANES spectra can be difficult to analyze fully. For other materials density functional theory calculations compared to near edge measurements have been a good way to understand the 3d valence electrons (2).

  6. Method of making a cathode from tungsten and iridium powders using a strontium peroxide containing material as the impregnant

    SciTech Connect

    Branovich, L.E.; Freeman, G.L.; Smith, B.

    1988-11-25

    This invention relates in general to a method of making a long-life high-current-density cathode and in particular, to a method of making such a cathode from a mixture of tungsten and iridium powders using a strontium peroxide containing material as the impregnant. The general object of this invention is to provide an improved method of making a long life high current density cathode. A more specific object of the invention is to provide such a method in which lower temperatures can be used than were used in S.N. 204,327 for the impregnation of the tungsten-iridium billet. It has now been found that the aforementioned objects can be attained by a method that uses a strontium peroxide-containing material as the impregnant. More particularly, according to the invention, a suitable porous billet of tungsten, or tungsten-iridium, or tungsten-osmium or tungsten-rhodium is impregnated with a strontium peroxide containing material in a hydrogen atmosphere and slowly heated to above 215 C to decompose the strontium peroxide, SrO/sub 2/ to form strontium oxide, SrO, and oxygen, O/sub 2/.

  7. Synthesis and characterization of nanostructured cathode materials for rechargeable lithium/lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Jingsi

    The rapidly increasing markets of portable electronic devices and electric/hybrid vehicles have raised worldwide R&D efforts in developing high-energy rechargeable lithium and lithium ion batteries. High performance intercalation cathodes are key to the success of these batteries. The nanotechnology has endowed the electrode materials with a variety of improved features as well as unique characteristics. Synthesis approaches were designed in this thesis work to utilize these advantages and investigate the exceptional phenomena raised by the nanostructured materials. A novel sol-gel method was designed for the synthesis of carbon-coated phase-pure lithium iron phosphate with submicron particle sizes and uniform size distribution. The surface carbon coating was formed in-situ through pyrolysis of the precursor gel, which improved the apparent electronic conductivity of the as prepared material to 10-2 S/cm compared with 10-9-10-10 S/cm of the pristine LiFePO 4. The favorable physical characteristics of the synthesized LiFePO 4 particles and the improved electronic conductivity through the carbon coating led to electrochemical properties comparable to the best performances reported so far. Amorphous manganese oxide cryogels with nanoarchitecture were obtained by freeze-drying Mn (IV) oxide hydrogels. The combination of the advantages of the amorphous structure and the nano-architecture of the materials gave high capacities and excellent rate capabilities. This work led to the finding of a nanocrystalline Li2MnO3-like compound with a surprising electrochemical activity, which is in sharp contrast to the microcrystalline rock-salt Li2MnO3 that has been known to be electrochemically inactive. The study highlights the possibility of qualitative difference in intercalation behavior of nanostructured intercalation compounds compared with their microcrystalline counterparts. Bismuth and copper modified amorphous manganese oxides were synthesized by aqueous coprecipitation

  8. Metallized graphite as an improved cathode material for aluminium/air batteries

    NASA Astrophysics Data System (ADS)

    Mukherjee, Ambick; N. Basumallick, Indra

    1993-06-01

    This paper reports the fabrication of metallized (Pt, Ni, Cu, Fe, Co) graphite cathodes by an electrodeposition method from an appropriate electrolytic bath, together with the performance characteristics of specially-designed aluminium/air cells that utilize these cathodes. In these cells, the aluminium electrodes were separated by a glass-jacket separator. The latter prevents mixing of hydrogen gas evolved due to the corrosion of the aluminium electrode. While the open-circuit voltage of the cells is virtually invariant, the short-circuit current and discharge behaviour are markedly dependent upon the choice of catalytic metal. The discharge profiles are improved markedly for cells with a Pt-, Ni- or Cu-coated graphite air cathode, but the reverse is found for Fe- and Co-coated cathodes. The behaviour is explained in terms of chemisorption and the better catalytic activity of Pt, Ni and Cu. These results suggest that Ni- and Cu-coated graphite air cathodes are promising low-cost and efficiennt electrodes for aluminium/air batteries.

  9. Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

    DOE PAGES

    Liu, Haodong; An, Ke; Venkatachalam, Subramanian; Qian, Danna; Zhang, Minghao; Meng, Ying Shirley

    2016-04-06

    Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix/3Ni(3/8-3x/8)Co(1/4-x/4)Mn(3/8+7x/24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix/3Ni(1/3-x/3)Co(1/3-x/3)Mn(1/3+x/3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presencemore » of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.« less

  10. One-step synthesis of graphene/polypyrrole nanofiber composites as cathode material for a biocompatible zinc/polymer battery.

    PubMed

    Li, Sha; Shu, Kewei; Zhao, Chen; Wang, Caiyun; Guo, Zaiping; Wallace, Gordon; Liu, Hua Kun

    2014-10-01

    The significance of developing implantable, biocompatible, miniature power sources operated in a low current range has become manifest in recent years to meet the demands of the fast-growing market for biomedical microdevices. In this work, we focus on developing high-performance cathode material for biocompatible zinc/polymer batteries utilizing biofluids as electrolyte. Conductive polymers and graphene are generally considered to be biocompatible and suitable for bioengineering applications. To harness the high electrical conductivity of graphene and the redox capability of polypyrrole (PPy), a polypyrrole fiber/graphene composite has been synthesized via a simple one-step route. This composite is highly conductive (141 S cm(-1)) and has a large specific surface area (561 m(2) g(-1)). It performs more effectively as the cathode material than pure polypyrrole fibers. The battery constructed with PPy fiber/reduced graphene oxide cathode and Zn anode delivered an energy density of 264 mWh g(-1) in 0.1 M phosphate-buffer saline.

  11. Ruthenium-oxide-coated sodium vanadium fluorophosphate nanowires as high-power cathode materials for sodium-ion batteries.

    PubMed

    Peng, Manhua; Li, Biao; Yan, Huijun; Zhang, Dongtang; Wang, Xiayan; Xia, Dingguo; Guo, Guangsheng

    2015-05-26

    Sodium-ion batteries are a very promising alternative to lithium-ion batteries because of their reliance on an abundant supply of sodium salts, environmental benignity, and low cost. However, the low rate capability and poor long-term stability still hinder their practical application. A cathode material, formed of RuO2 -coated Na3 V2 O2 (PO4 )2 F nanowires, has a 50 nm diameter with the space group of I4/mmm. When used as a cathode material for Na-ion batteries, a reversible capacity of 120 mAh g(-1) at 1 C and 95 mAh g(-1) at 20 C can be achieved after 1000 charge-discharge cycles. The ultrahigh rate capability and enhanced cycling stability are comparable with high performance lithium cathodes. Combining first principles computational investigation with experimental observations, the excellent performance can be attributed to the uniform and highly conductive RuO2 coating and the preferred growth of the (002) plane in the Na3 V2 O2 (PO4 )2 F nanowires. PMID:25864686

  12. Ruthenium-oxide-coated sodium vanadium fluorophosphate nanowires as high-power cathode materials for sodium-ion batteries.

    PubMed

    Peng, Manhua; Li, Biao; Yan, Huijun; Zhang, Dongtang; Wang, Xiayan; Xia, Dingguo; Guo, Guangsheng

    2015-05-26

    Sodium-ion batteries are a very promising alternative to lithium-ion batteries because of their reliance on an abundant supply of sodium salts, environmental benignity, and low cost. However, the low rate capability and poor long-term stability still hinder their practical application. A cathode material, formed of RuO2 -coated Na3 V2 O2 (PO4 )2 F nanowires, has a 50 nm diameter with the space group of I4/mmm. When used as a cathode material for Na-ion batteries, a reversible capacity of 120 mAh g(-1) at 1 C and 95 mAh g(-1) at 20 C can be achieved after 1000 charge-discharge cycles. The ultrahigh rate capability and enhanced cycling stability are comparable with high performance lithium cathodes. Combining first principles computational investigation with experimental observations, the excellent performance can be attributed to the uniform and highly conductive RuO2 coating and the preferred growth of the (002) plane in the Na3 V2 O2 (PO4 )2 F nanowires.

  13. Facile preparation of core@shell and concentration-gradient spinel particles for Li-ion battery cathode materials

    NASA Astrophysics Data System (ADS)

    Kozawa, Takahiro; Naito, Makio

    2015-02-01

    Core@shell and concentration-gradient particles have attracted much attention as improved cathodes for Li-ion batteries (LIBs). However, most of their preparation routes have employed a precisely-controlled co-precipitation method. Here, we report a facile preparation route of core@shell and concentration-gradient spinel particles by dry powder processing. The core@shell particles composed of the MnO2 core and the Li(Ni,Mn)2O4 spinel shell are prepared by mechanical treatment using an attrition-type mill, whereas the concentration-gradient spinel particles with an average composition of LiNi0.32Mn1.68O4 are produced by calcination of their core@shell particles as a precursor. The concentration-gradient LiNi0.32Mn1.68O4 spinel cathode exhibits the high discharge capacity of 135.3 mA h g-1, the wide-range plateau at a high voltage of 4.7 V and the cyclability with a capacity retention of 99.4% after 20 cycles. Thus, the facile preparation route of the core@shell and concentration-gradient particles may provide a new opportunity for the discovery and investigation of functional materials as well as for the cathode materials for LIBs.

  14. One-step synthesis of graphene/polypyrrole nanofiber composites as cathode material for a biocompatible zinc/polymer battery.

    PubMed

    Li, Sha; Shu, Kewei; Zhao, Chen; Wang, Caiyun; Guo, Zaiping; Wallace, Gordon; Liu, Hua Kun

    2014-10-01

    The significance of developing implantable, biocompatible, miniature power sources operated in a low current range has become manifest in recent years to meet the demands of the fast-growing market for biomedical microdevices. In this work, we focus on developing high-performance cathode material for biocompatible zinc/polymer batteries utilizing biofluids as electrolyte. Conductive polymers and graphene are generally considered to be biocompatible and suitable for bioengineering applications. To harness the high electrical conductivity of graphene and the redox capability of polypyrrole (PPy), a polypyrrole fiber/graphene composite has been synthesized via a simple one-step route. This composite is highly conductive (141 S cm(-1)) and has a large specific surface area (561 m(2) g(-1)). It performs more effectively as the cathode material than pure polypyrrole fibers. The battery constructed with PPy fiber/reduced graphene oxide cathode and Zn anode delivered an energy density of 264 mWh g(-1) in 0.1 M phosphate-buffer saline. PMID:25198621

  15. Inverse vulcanization of sulfur with divinylbenzene: Stable and easy processable cathode material for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Gomez, Iñaki; Mecerreyes, David; Blazquez, J. Alberto; Leonet, Olatz; Ben Youcef, Hicham; Li, Chunmei; Gómez-Cámer, Juan Luis; Bundarchuk, Oleksandr; Rodriguez-Martinez, Lide

    2016-10-01

    Lithium-Sulfur (Li-S) battery technology is one of the promising candidates for next generation energy storage systems. Many studies have focused on the cathode materials to improve the cell performance. In this work we present a series of poly (S-DVB) copolymers synthesised by inverse vulcanization of sulfur with divinylbenzene (DVB). The poly (S-DVB) cathode shows excellent cycling performances at C/2 and C/4 current rates, respectively. It was demonstrated poly (S-DVB) copolymer containing 20% DVB did not influence the electrochemical performance of the sulfur material, compared to elemental sulfur as high specific capacities over ∼700 mAh g-1 at 500 cycles were achieved at C/4 current rate, comparable to conventional carbon-based S cathodes. However, the use of copolymer network is assumed to act firstly as sulfur reservoir and secondly as mechanical stabilizer, enhancing significantly the cycling lifetime. The Li-poly (S-DVB) cell demonstrated an extremely low degradation rate of 0.04% per cycle achieving over 1600 cycles at C/2 current rate.

  16. Facile electrochemical polymerization of polypyrrole film applied as cathode material in dual rotating disk photo fuel cell

    NASA Astrophysics Data System (ADS)

    Li, Kan; Zhang, Hongbo; Tang, Tiantian; Tang, Yanping; Wang, Yalin; Jia, Jinping

    2016-08-01

    Polypyrrole (PPy) film is synthesized on Ti substrate through electrochemical polymerization method and is applied as cathode material in a TiO2 NTs-PPy dual rotating disk photo fuel cell (PFC). The optimized PPy electrochemical polymerization is carried out using linear sweep voltammetry from 0 V to 1.2 V (vs. SCE) with scan rate of 0.1 V s-1, 100 circles. Sixty milliliter real textile wastewater with the initial COD and conductivity of 408 ± 6 mgO2 L-1 and 20180 μS cm-1 is treated in this PFC under UV irradiation. About 0.46 V open-circuit voltage (VOC) and 1.8-2.2 mA short-circuit current (JSC) are obtained. Due to the effective electron-hole separation effect, the COD removal rate is as high as 0.0055 min-1. Stable current and COD removal can be obtained at different output voltage. Two influence factors including rotating speed and pH are investigated. Better electricity generation performance and COD removal activity are achieved at high rotating speed and in acidic condition. In comparison with platinized cathode, though VOC is lower, similar JSC is measured. Considering the high cost of Pt, PPy is a promising alternative cathode material in PFC that can also generate electricity efficiently and stably.

  17. Facile electrochemical polymerization of polypyrrole film applied as cathode material in dual rotating disk photo fuel cell

    NASA Astrophysics Data System (ADS)

    Li, Kan; Zhang, Hongbo; Tang, Tiantian; Tang, Yanping; Wang, Yalin; Jia, Jinping

    2016-08-01

    Polypyrrole (PPy) film is synthesized on Ti substrate through electrochemical polymerization method and is applied as cathode material in a TiO2 NTs-PPy dual rotating disk photo fuel cell (PFC). The optimized PPy electrochemical polymerization is carried out using linear sweep voltammetry from 0 V to 1.2 V (vs. SCE) with scan rate of 0.1 V s-1, 100 circles. Sixty milliliter real textile wastewater with the initial COD and conductivity of 408 ± 6 mgO2 L-1 and 20180 μS cm-1 is treated in this PFC under UV irradiation. About 0.46 V open-circuit voltage (VOC) and 1.8-2.2 mA short-circuit current (JSC) are obtained. Due to the effective electron-hole separation effect, the COD removal rate is as high as 0.0055 min-1. Stable current and COD removal can be obtained at different output voltage. Two influence factors including rotating speed and pH are investigated. Better electricity generation performance and COD removal activity are achieved at high rotating speed and in acidic condition. In comparison with platinized cathode, though VOC is lower, similar JSC is measured. Considering the high cost of Pt, PPy is a promising alternative cathode material in PFC that can also generate electricity efficiently and stably.

  18. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability.

    PubMed

    Wang, Hailiang; Yang, Yuan; Liang, Yongye; Robinson, Joshua Tucker; Li, Yanguang; Jackson, Ariel; Cui, Yi; Dai, Hongjie

    2011-07-13

    We report the synthesis of a graphene-sulfur composite material by wrapping poly(ethylene glycol) (PEG) coated submicrometer sulfur particles with mildly oxidized graphene oxide sheets decorated by carbon black nanoparticles. The PEG and graphene coating layers are important to accommodating volume expansion of the coated sulfur particles during discharge, trapping soluble polysulfide intermediates, and rendering the sulfur particles electrically conducting. The resulting graphene-sulfur composite showed high and stable specific capacities up to ∼600 mAh/g over more than 100 cycles, representing a promising cathode material for rechargeable lithium batteries with high energy density.

  19. Cathode materials for lithium-ion batteries: Synthesis, analysis, and thermal studies

    NASA Astrophysics Data System (ADS)

    Kim, Jeom-Soo

    2001-12-01

    The effect of synthesis technique was studied with two representative techniques such as solid-state reaction (SSR) and sol-gel methods used for LixMn2O4 (x = 1.03) preparation. For the in-cell performance of LixMn2O4 as electrode material, variation in processing temperature and intermittent grinding were found to be the key parameters of synthesis. The characteristics of powder synthesized by these different methods were investigated and compared with stoichiometric LiMn2O4 spinel using a combination of physicochemical and electrochemical techniques. Physicochemical characteristics investigated including phase identification, particle size, density, BET surface area, and composition. The electrochemical performance was characterized with 2016 coin type cells, using a battery tester. In addition, the electro-analytical response was studied using slow sweep cyclic voltammetry (SSCV) and current pulse response (CPR). The hybrid pulse power characterization (HPPC), one of the test profiles proposed by the Partnership for New Generation Vehicle (PNGV), was applied to check the possibility of using LixMn 2O4 electrodes in HEV batteries. Chemical diffusion coefficients of lithium (D Li+) in spinel LixMn2O 4 were measured by various electrochemical techniques such as potentiostatic intermittent titration technique (PITT), electrochemical impedance spectroscopy (EIS), and galvanostatic intermittent titration technique (GITT). DLi+ varied with x in LixMn2O4, showing strong dependence on the concentration of lithium. The thermal behavior of major cathode materials for Li-ion battery (LiCoO 2, LiNi0.8Co0.2O2, and LiMn2O 4) was investigated using an isothermal microcalorimeter, in combination with a battery tester. The total heat generation rate was found to be dependent on the concentration of lithium in LixMn2O4 and LixCoO2 while it was relatively constant in the case of LixNi0.8Co0.2O2. The area-specific impedance (ASI) measured in these tests indicated that the heat

  20. Dependence of structure and temperature for lithium-rich layered-spinel microspheres cathode material of lithium ion batteries.

    PubMed

    Wang, Di; Yu, Ruizhi; Wang, Xianyou; Ge, Long; Yang, Xiukang

    2015-02-12

    Homogeneous lithium-rich layered-spinel 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 microspheres (~1 μm) are successfully prepared by a solvothermal method and subsequent high-temperature calcinations process. The effects of temperature on the structure and performance of the as-prepared cathode material are systemically studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatical charge/discharge and electrochemical impedance spectra. The results show that a spinel Li4Mn5O12 component can be controllably introduced into the lithium-rich layered material at 750°C. Besides, it has been found that the obtained layered-spinel cathode material represents excellent electrochemical characteristics. For example, it can deliver a high initial discharge capacity of 289.6 mAh g(-1) between 2.0 V and 4.6 V at a rate of 0.1 C at room temperature, and a discharge capacity of 144.9 mAh g(-1) at 5 C and 122.8 mAh g(-1) even at 10 C. In addition, the retention of the capacity is still as high as 88% after 200 cycles, while only 79.9% for the single-phase layered material. The excellent electrochemical performance of the as-prepared cathode material can probably be attributed to the hybrid structures combining a fast Li-ion diffusion rate of 3D spinel Li4Mn5O12 phase and a high capacity of the layered Li-Mn-Ni-Co-O component.

  1. Dependence of structure and temperature for lithium-rich layered-spinel microspheres cathode material of lithium ion batteries

    PubMed Central

    Wang, Di; Yu, Ruizhi; Wang, Xianyou; Ge, Long; Yang, Xiukang

    2015-01-01

    Homogeneous lithium-rich layered-spinel 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 microspheres (~1 μm) are successfully prepared by a solvothermal method and subsequent high-temperature calcinations process. The effects of temperature on the structure and performance of the as-prepared cathode material are systemically studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatical charge/discharge and electrochemical impedance spectra. The results show that a spinel Li4Mn5O12 component can be controllably introduced into the lithium-rich layered material at 750°C. Besides, it has been found that the obtained layered-spinel cathode material represents excellent electrochemical characteristics. For example, it can deliver a high initial discharge capacity of 289.6 mAh g−1 between 2.0 V and 4.6 V at a rate of 0.1 C at room temperature, and a discharge capacity of 144.9 mAh g−1 at 5 C and 122.8 mAh g−1 even at 10 C. In addition, the retention of the capacity is still as high as 88% after 200 cycles, while only 79.9% for the single-phase layered material. The excellent electrochemical performance of the as-prepared cathode material can probably be attributed to the hybrid structures combining a fast Li-ion diffusion rate of 3D spinel Li4Mn5O12 phase and a high capacity of the layered Li-Mn-Ni-Co-O component. PMID:25672573

  2. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; Zhou, Haoshen; Okabayashi, Jun; Ban, Chunmei; Glans, Per-Anders; Guo, Jinghua; Mizokawa, Takashi; Chen, Gang; Achkar, Andrew J.; Hawthron, David G.; Regier, Thomas Z.; Wadati, Hiroki

    2016-03-01

    We evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathode materials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi0.5Mn1.5O4, the line shape of the Mn L3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathode materials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are useful enough for the Ni L edge which is far from the O K edge.

  3. Nickel Hydroxide-Modified Sulfur/Carbon Composite as a High-Performance Cathode Material for Lithium Sulfur Battery.

    PubMed

    Niu, Xiao-Qing; Wang, Xiu-Li; Xie, Dong; Wang, Dong-Huang; Zhang, Yi-Di; Li, Yi; Yu, Ting; Tu, Jiang-Ping

    2015-08-01

    Tailored sulfur cathode is vital for the development of a high performance lithium-sulfur (Li-S) battery. A surface modification on the sulfur/carbon composite would be an efficient strategy to enhance the cycling stability. Herein, we report a nickel hydroxide-modified sulfur/conductive carbon black composite (Ni(OH)2@S/CCB) as the cathode material for the Li-S battery through the thermal treatment and chemical precipitation method. In this composite, the sublimed sulfur is stored in the CCB, followed by a surface modification of Ni(OH)2 nanoparticles with size of 1-2 nm. As a cathode for the Li-S battery, the as-prepared Ni(OH)2@S/CCB electrode exhibits better cycle stability and higher rate discharge capacity, compared with the bare S/CCB electrode. The improved performance is largely due to the introduction of Ni(OH)2 surface modification, which can effectively suppress the "shuttle effect" of polysulfides, resulting in enhanced cycling life and higher capacity. PMID:26158375

  4. Graphene–Selenium Hybrid Microballs as Cathode Materials for High-performance Lithium–Selenium Secondary Battery Applications

    NASA Astrophysics Data System (ADS)

    Youn, Hee-Chang; Jeong, Jun Hui; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-08-01

    In this study, graphene–selenium hybrid microballs (G–SeHMs) are prepared in one step by aerosol microdroplet drying using a commercial spray dryer, which represents a simple, scalable continuous process, and the potential of the G–SeHMs thus prepared is investigated for use as cathode material in applications of lithium–selenium secondary batteries. These morphologically unique graphene microballs filled with Se particles exhibited good electrochemical properties, such as high initial specific capacity (642 mA h g‑1 at 0.1 C, corresponding to Se electrochemical utilisation as high as 95.1%), good cycling stability (544 mA h g‑1 after 100 cycles at 0.1 C 84.5% retention) and high rate capability (specific capacity of 301 mA h g‑1 at 5 C). These electrochemical properties are attributed to the fact that the G–SeHM structure acts as a confinement matrix for suppressing the dissolution of polyselenides in the organic electrolyte, as well as an electron conduction path for increasing the transport rate of electrons for electrochemical reactions. Notably, based on the weight of hybrid materials, electrochemical performance is considerably better than that of previously reported Se-based cathode materials, attributed to the high Se loading content (80 wt%) in hybrid materials.

  5. Graphene–Selenium Hybrid Microballs as Cathode Materials for High-performance Lithium–Selenium Secondary Battery Applications

    PubMed Central

    Youn, Hee-Chang; Jeong, Jun Hui; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-01-01

    In this study, graphene–selenium hybrid microballs (G–SeHMs) are prepared in one step by aerosol microdroplet drying using a commercial spray dryer, which represents a simple, scalable continuous process, and the potential of the G–SeHMs thus prepared is investigated for use as cathode material in applications of lithium–selenium secondary batteries. These morphologically unique graphene microballs filled with Se particles exhibited good electrochemical properties, such as high initial specific capacity (642 mA h g−1 at 0.1 C, corresponding to Se electrochemical utilisation as high as 95.1%), good cycling stability (544 mA h g−1 after 100 cycles at 0.1 C; 84.5% retention) and high rate capability (specific capacity of 301 mA h g−1 at 5 C). These electrochemical properties are attributed to the fact that the G–SeHM structure acts as a confinement matrix for suppressing the dissolution of polyselenides in the organic electrolyte, as well as an electron conduction path for increasing the transport rate of electrons for electrochemical reactions. Notably, based on the weight of hybrid materials, electrochemical performance is considerably better than that of previously reported Se-based cathode materials, attributed to the high Se loading content (80 wt%) in hybrid materials. PMID:27480798

  6. Graphene-Selenium Hybrid Microballs as Cathode Materials for High-performance Lithium-Selenium Secondary Battery Applications.

    PubMed

    Youn, Hee-Chang; Jeong, Jun Hui; Roh, Kwang Chul; Kim, Kwang-Bum

    2016-01-01

    In this study, graphene-selenium hybrid microballs (G-SeHMs) are prepared in one step by aerosol microdroplet drying using a commercial spray dryer, which represents a simple, scalable continuous process, and the potential of the G-SeHMs thus prepared is investigated for use as cathode material in applications of lithium-selenium secondary batteries. These morphologically unique graphene microballs filled with Se particles exhibited good electrochemical properties, such as high initial specific capacity (642 mA h g(-1) at 0.1 C, corresponding to Se electrochemical utilisation as high as 95.1%), good cycling stability (544 mA h g(-1) after 100 cycles at 0.1 C; 84.5% retention) and high rate capability (specific capacity of 301 mA h g(-1) at 5 C). These electrochemical properties are attributed to the fact that the G-SeHM structure acts as a confinement matrix for suppressing the dissolution of polyselenides in the organic electrolyte, as well as an electron conduction path for increasing the transport rate of electrons for electrochemical reactions. Notably, based on the weight of hybrid materials, electrochemical performance is considerably better than that of previously reported Se-based cathode materials, attributed to the high Se loading content (80 wt%) in hybrid materials. PMID:27480798

  7. The Influences of different cathode materials on Tris-(8-Hydroxyquinoline)- Aluminum Doped with CsNO3 in Organic Light emitting Devices

    NASA Astrophysics Data System (ADS)

    Chen, Mei-Hsin; Lu, Yin-Jui; Wu, Chung-Chih; Wu, Chih-I.

    2008-03-01

    This paper presents the investigations of interfacial interactions and electron-injection mechanisms between cesium nitrate (CsNO3) and different cathode materials. By using ultraviolet and x-ray photoemission spectroscopy, the properties of electronic structures and the interfacial chemistry are studied. According to our results, there exists a phenomenon of electron exchange at the interface results in changes of Aluminum 2s core level binding energy by 1 eV when aluminum was deposited on CsNO3. This means electrons transfer from cathode materials to the surface of CsNO3, forming a strong dipolar field at the interface and reduction of the electron injection barrier. But, in contract, there exists nearly no reaction between CsNO3 and silver cathode. The evidences show that CsNO3 is more effective only with aluminum cathode due to a reaction between Aluminum, Cesium and Nitrogen atoms.

  8. Effect of Transition Metal Ordering on the Electronic Properties of LiNi1 - y - xCoyMnxO2 Cathode Materials for Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Longo, Roberto; Kong, Fantai; Kc, Santosh; Yeon, Dong-Hee; Yoon, Jaegu; Park, Jin-Hwan; Doo, Seok-Kwang; Cho, Kyeongjae; MSL Team; SAIT Team

    2015-03-01

    Current Li-ion batteries use layered oxides as cathode materials, specially LiCoO2 or LiNi1 - y - xCoyMnxO2(NCM), and graphite as anode. Co layered oxides suffer from the high cost and toxicity of cobalt, together with certain instability at high operational temperatures. To overcome these difficulties, the synthesis of novel materials composed of layered oxides with different sets of Transition Metals (TM) has become the most successful way to solve the particular drawbacks of every single-oxide family. Although layered materials can deliver larger capacity than other families of cathode materials, the energy density has yet to be increased in order to match the expectations deposited on the NCM oxides. To acquire a high capacity, they need to be cycled at high operational voltages, resulting in voltage and capacity fading over a large number of cycles. In this work, we examine the phase diagram of the Li-Ni-Co-Mn-O system and the effect of TM ordering on the electronic properties of NCM cathode materials, using density-functional theory. Our findings will provide conceptual guidance in the experimental search for the mechanisms driving the voltage and capacity fading of the NCM family of cathode materials, in an attempt to solve such structural instability problems and, thus, improving the performance of the NCM cathode materials. This work was supported by Samsung GRO project.

  9. Preliminary study of structural changes in Li2MnSiO4 cathode material during electrochemical reaction

    NASA Astrophysics Data System (ADS)

    Świętosławski, Michał; Molenda, Marcin; Gajewska, Marta

    2016-06-01

    In this paper, we present exsitu observations of a structure of particular Li2MnSiO4 grains at different states of charge (SOC). The goal of these studies is structural analysis of Li2MnSiO4 cathode material for Li-ion batteries at different stages of electrochemical reaction using transmission electron microscopy. Performed analysis suggests that amorphization process of Li2MnSiO4 is not directly connected with lithium ions deintercalation but with additional electrochemical reactions running in the working cell.

  10. Thermal Stability of FeS2 Cathode Material in "Thermal" Batteries: Effect of Dissolved Oxides in Molten Salt Electrolytes

    NASA Astrophysics Data System (ADS)

    Masset, Patrick J.

    2008-09-01

    The thermal stability of FeS2 cathode material for thermal batteries is investigated in the LiCl-KCl eutectic containing up to 10 wt% Li2O (used as anti-peak). The results show that the decomposition of pyrite shifts to higher temperatures in the presence of molten salts as the S2 gas is repressed by the liquid phase. For high lithium oxide contents the decomposition temperature of pyrite decreases by 100 °C. In addition Li2FeS2 as reaction product is evidenced whereas Li3Fe2S4 is expected from literature data.

  11. Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

    SciTech Connect

    Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung-Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao-Qing

    2014-12-18

    For LiMO2 (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li2MoO3). A ‘unit cell breathing’ mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in ‘normal’ materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.

  12. Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung-Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao-Qing

    2014-11-01

    For LiMO2 (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li2MoO3). A ‘unit cell breathing’ mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal-metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in ‘normal’ materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.

  13. Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

    SciTech Connect

    Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung -Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao -Qing

    2014-11-18

    Through a systematic study of lithium molybdenum trioxide (Li2MoO3), a new ‘unit cell breathing’ mechanism is introduced based on both crystal and electronic structural changes of transition metal oxide cathode materials during charge–discharge: For widely used LiMO2 (M = Co, Ni, Mn), lattice parameters, a and b, contracts during charge. However, for Li2MoO3, such changes are in opposite directions. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of M–M bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking M–O as controlling factor in ‘normal’ materials. The cation mixing caused by migration of Mo ions at higher oxidation state provides the benefits of reducing the c expansion range in early stage of charging and suppressing the structure collapse at high voltage charge. These results open a new strategy for designing and engineering layered cathode materials for high energy density lithium-ion batteries.

  14. Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

    DOE PAGES

    Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung -Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao -Qing

    2014-11-18

    Through a systematic study of lithium molybdenum trioxide (Li2MoO3), a new ‘unit cell breathing’ mechanism is introduced based on both crystal and electronic structural changes of transition metal oxide cathode materials during charge–discharge: For widely used LiMO2 (M = Co, Ni, Mn), lattice parameters, a and b, contracts during charge. However, for Li2MoO3, such changes are in opposite directions. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of M–M bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking M–O as controlling factor in ‘normal’ materials.more » The cation mixing caused by migration of Mo ions at higher oxidation state provides the benefits of reducing the c expansion range in early stage of charging and suppressing the structure collapse at high voltage charge. These results open a new strategy for designing and engineering layered cathode materials for high energy density lithium-ion batteries.« less

  15. Cathode material comparison of thermal runaway behavior of Li-ion cells at different state of charges including over charge

    NASA Astrophysics Data System (ADS)

    Mendoza-Hernandez, Omar Samuel; Ishikawa, Hiroaki; Nishikawa, Yuuki; Maruyama, Yuki; Umeda, Minoru

    2015-04-01

    The analysis of Li-ion secondary cells under outstanding conditions, as overcharge and high temperatures, is important to determine thermal abuse characteristics of electroactive materials and precise risk assessments on Li-ion cells. In this work, the thermal runaway behavior of LiCoO2 and LiMn2O4 cathode materials were compared at different state of charges (SOCs), including overcharge, by carrying out accelerating rate calorimetry (ARC) measurements using 18650 Li-ion cells. Onset temperatures of self-heating reactions and thermal runaway behavior were identified, and by using these onset points thermal mapping plots were made. We were able to identify non-self-heating, self-heating and thermal runaway regions as a function of state of charge and temperature. The cell using LiMn2O4 cathode material was found to be more thermally stable than the cell using LiCoO2. In parallel with the ARC measurements, the electrochemical behavior of the cells was monitored by measuring the OCV and internal resistance of the cells. The electrochemical behavior of the cells showed a slightly dependency on SOC.

  16. Effect of surfactants on the electrochemical behavior of LiFePO4 cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Mandal, B. P.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2014-11-01

    The application of lithium iron phosphate as positive electrode material for lithium ion batteries has been challenged by its poor electronic conductivity. To improve its conductivity and electrochemical performance, we have synthesized LiFePO4/C composite cathode materials by sol gel technique using long chain fatty acids, such as, lauric, myristic, and oleic acids, as surfactants for carbon coating. The phase purity of the three LiFePO4/C composites was confirmed by X-ray diffraction. The Raman spectroscopy, scanning electron microscopy and transmission electron microscopy measurements show that the surfactants coat the LiFePO4 particles with carbon with varying degree of uniformity depending on the surfactant used. The sample prepared in presence of lauric acid shows smaller particle size and the lowest charge transfer resistance, higher Li-ion diffusion coefficient, higher discharge capacity (∼155 mAh g-1 at C/3 rate), better rate capability and cyclic stability compared to the other two samples. We found the smaller particle size, uniformity of carbon coating, reduced agglomeration, and a lower amount of Fe3+ impurity phase in the samples to be major contributing factors for better electrochemical properties in the LiFePO4/C cathode material.

  17. Synthesis of FePO{sub 4} cathode material for lithium ion batteries by a sonochemical method

    SciTech Connect

    Okawa, Hirokazu Yabuki, Junpei; Kawamura, Youhei; Arise, Ichiro; Sato, Mineo

    2008-05-06

    Hydrated amorphous FePO{sub 4} was synthesized by a sonochemical reaction method, in which a solution of (NH{sub 4}){sub 2}HPO{sub 4} and FeSO{sub 4}.7H{sub 2}O was irradiated by an ultrasonic wave. From this material, two kinds of cathode materials were easily prepared: (1) an amorphous sample prepared by heating at 350 deg. C and (2) a crystalline sample prepared by heating at 700 deg. C. Both samples consisted of homogeneous sub-micron particles. The amorphous sample of FePO{sub 4} exhibited high discharge capacities with more than 100 mAh g{sup -1} in the range of 3.9-2.0 V versus Li/Li{sup +} at a current rate of 0.2 C. The sonochemical synthesis proposed herein has the following advantages: no use of oxidation agents for production of trivalent iron ions, reduction in reaction time, control of particle size, and enlargement in surface area for the preparation of the cathode material.

  18. Thermal and electrochemical properties of PEO-LiTFSI-Pyr14TFSI-based composite cathodes, incorporating 4 V-class cathode active materials

    NASA Astrophysics Data System (ADS)

    Wetjen, Morten; Kim, Guk-Tae; Joost, Mario; Appetecchi, Giovanni B.; Winter, Martin; Passerini, Stefano

    2014-01-01

    Poly(ethylene oxide)-lithium bis(trifluoromethanesulfonyl)imide N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PEO-LiTFSI-Pyr14TFSI)-based 4 V-class composite cathodes, incorporating either Li(Ni1/3Co1/3Mn1/3)O2 or Li(Ni0.8Co0.15Al0.05)O2 were prepared by a hot-pressing process and successively investigated in terms of their morphological, thermal, and electrochemical properties. Thereby, excellent mechanical and thermal properties could be demonstrated for all composite cathodes. The electrochemical performance of truly dry all-solid-state Li/P(EO)10LiTFSI-(Pyr14TFSI)2/composite cathode batteries at temperatures as low as 40 °C revealed high delivered capacities. However, in comparison with LiFePO4, the 4 V-class composite cathodes also indicated much lower capacity retention. In-depth investigations on the interfacial properties of Li(Ni0.8Co0.15Al0.05)O2 composite cathodes revealed a strong dependence on the anodic cut-off potential and the presence of current flow through the cell, whereby different degradation mechanisms could be characterized upon cycling, according to which the finite growth of a surface films at both electrode/polymer electrolyte interfaces inhibited continuous decomposition of the polymer electrolyte even at potentials as high as 4.3 V. Moreover, the presence of Pyr14TFSI in the 4 V-class composite cathodes sustainably reduced the cathode interfacial resistance and presumably diminished the corrosion of the aluminum current collector.

  19. Preparation for CeO2/Nanographite Composite Materials and Electrochemical Degradation of Phenol by CeO2/Nanographite Cathodes.

    PubMed

    Yu, Li; Yu, Xiujuan; Sun, Tianyi; Wang, Na

    2015-07-01

    CeO2/nanographite (CeO2/nano-G) composite materials were got by chemical precipitation method with nanographite (nano-G) and cerous nitrate hexahydrate as raw materials. The microstructures of CeO2/nano-G composite materials were characterized by means of SEM, XRD, XPS and Raman. The cathodes were made by nano-G and CeO2/nano-G composite materials, respectively. The electrolysis phenol was conducted by the diaphragm cell prepared cathode and the Ti/RuO2 anode. The results indicated that the Cerium oxide is mainly in nanoscale spherical state, uniformly dispersed in the nanographite sheet surface, and there are two different oxidation states for elemental Ce, namely, Ce(III) and Ce(IV). In the diaphragm electrolysis system with the aeration conditions, the degradation rate of phenol reached 93.9% under 120 min's electrolysis. Ceria in the cathode materials might lead to an increase in the local oxygen concentration, which accelerated the two-electron reduction of O2 to hydrogen peroxide (H2O2). The removal efficiency of phenol by using the CeO2/nano-G composite cathode was better than that of the nano-G cathode.

  20. Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2015-11-01

    This work is focussed on the processing of cathodic active material of spent lithium ion batteries (LIBs) to ensure resource recovery and minimize environmental degradation. The sulfuric acid leaching of metals was carried out for the recovery of all the valuable metals including nickel and manganese along with the frequently targeted metals like lithium and cobalt. The process parameters such as acid concentration, pulp density, time and temperature for the leaching of metals from the cathode powder containing 35.8% Co, 6.5% Li, 11.6% Mn and 10.06% Ni, were optimized. Results show the optimized leach recovery of 93.4% Li, 66.2% Co, 96.3% Ni and 50.2% Mn when the material was leached in 1M H2SO4 at 368 K and 50 g/L pulp density for 240 min. The need of a reductant for improved recovery of cobalt and manganese has been explained by the thermodynamic analysis (Eh-pH diagram) for these metals. Leaching of the valuable metals was found to follow the logarithmic rate law controlled by surface layer diffusion of the lixiviant reacting with the particles. The mode of leaching of the metals from the spent LIBs was further examined by chemical analysis of the samples at various stage of processing which was further corroborated by characterizing the untreated sample and the leach residues by XRD phase identification and the SEM-EDS studies.

  1. Single crystalline VO2 nanosheets: A cathode material for sodium-ion batteries with high rate cycling performance

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Jiang, Bo; Hu, Liwen; Lin, Zheshuai; Hou, Jungang; Jiao, Shuqiang

    2014-03-01

    In recent years, with the growing demands for large-scale applications of rechargeable batteries, the eco-friendly sodium-ion batteries with low price and high charge-discharge rates have attracted much attention. In this work, using a simple hydrothermal process, we successfully synthesize single crystalline VO2 parallel ultrathin nanosheets for the cathode material in sodium-ion batteries. Combined the XRD, XPS, electrochemical measurements with the first-principles simulations, the charge-discharge performance and the mechanism of Na insertion and extraction into/from the VO2 structure have systematically studied. The results reveal that the NaxVO2 products possess semiconductor properties and the interlayer distance almost keeps constant during charge and discharge process, which is beneficial to the transmission of Na ions. The charge and discharge process occurs between Na0.3VO2 and NaVO2. Even at a large current density of 500 mA g-1, the discharge capacity can still keep at 108 mAh g-1. As a cathode material for sodium-ion batteries, the results are outstanding and provide a possibility of large-scale applications for rechargeable sodium-ion batteries.

  2. Optimization of a microbial fuel cell for wastewater treatment using recycled scrap metals as a cost-effective cathode material.

    PubMed

    Lefebvre, Olivier; Tan, Zi; Shen, Yujia; Ng, How Y

    2013-01-01

    Microbial fuel cell (MFC) for wastewater treatment is still hindered by the prohibitive cost of cathode material, especially when platinum is used to catalyze oxygen reduction. In this study, recycled scrap metals could be used efficiently as cathode material in a specially-designed MFC. In terms of raw power, the scrap metals ranked as follows: W/Co > Cu/Ni > Inconel 718 > carpenter alloy; however, in terms of cost and long term stability, Inconel 718 was the preferred choice. Treatment performance--assessed on real and synthetic wastewater--was considerably improved either by filling the anode compartment with carbon granules or by operating the MFC in full-loop mode. The latter option allowed reaching 99.7% acetate removal while generating a maximum power of 36 W m(-3) at an acetate concentration of 2535 mg L(-1). Under these conditions, the energy produced by the system averaged 0.1 kWh m(-3) of wastewater treated. PMID:23138054

  3. High performance LiMn2O4 cathode materials grown with epitaxial layered nanostructure for Li-ion batteries.

    PubMed

    Lee, Min-Joon; Lee, Sanghan; Oh, Pilgun; Kim, Youngsik; Cho, Jaephil

    2014-02-12

    Tremendous research works have been done to develop better cathode materials for a large scale battery to be used for electric vehicles (EVs). Spinel LiMn2O4 has been considered as the most promising cathode among the many candidates due to its advantages of high thermal stability, low cost, abundance, and environmental affinity. However, it still suffers from the surface dissolution of manganese in the electrolyte at elevated temperature, especially above 60 °C, which leads to a severe capacity fading. To overcome this barrier, we here report an imaginative material design; a novel heterostructure LiMn2O4 with epitaxially grown layered (R3̅m) surface phase. No defect was observed at the interface between the host spinel and layered surface phase, which provides an efficient path for the ionic and electronic mobility. In addition, the layered surface phase protects the host spinel from being directly exposed to the highly active electrolyte at 60 °C. The unique characteristics of the heterostructure LiMn2O4 phase exhibited a discharge capacity of 123 mAh g(-1) and retained 85% of its initial capacity at the elevated temperature (60 °C) after 100 cycles.

  4. Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

    PubMed

    Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

    2014-01-01

    The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

  5. Iron-rich nanoparticle encapsulated, nitrogen doped porous carbon materials as efficient cathode electrocatalyst for microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Lu, Guolong; Zhu, Youlong; Lu, Lu; Xu, Kongliang; Wang, Heming; Jin, Yinghua; Jason Ren, Zhiyong; Liu, Zhenning; Zhang, Wei

    2016-05-01

    Developing efficient, readily available, and sustainable electrocatalysts for oxygen reduction reaction (ORR) in neutral medium is of great importance to practical applications of microbial fuel cells (MFCs). Herein, a porous nitrogen-doped carbon material with encapsulated Fe-based nanoparticles (Fe-Nx/C) has been developed and utilized as an efficient ORR catalyst in MFCs. The material was obtained through pyrolysis of a highly porous organic polymer containing iron(II) porphyrins. The characterizations of morphology, crystalline structure and elemental composition reveal that Fe-Nx/C consists of well-dispersed Fe-based nanoparticles coated by N-doped graphitic carbon layer. ORR catalytic performance of Fe-Nx/C has been evaluated through cyclic voltammetry and rotating ring-disk electrode measurements, and its application as a cathode electrocatalyst in an air-cathode single-chamber MFC has been investigated. Fe-Nx/C exhibits comparable or better performance in MFCs than 20% Pt/C, displaying higher cell voltage (601 mV vs. 591 mV), maximum power density (1227 mW m-2 vs. 1031 mW m-2) and Coulombic efficiency (50% vs. 31%). These findings indicate that Fe-Nx/C is more tolerant and durable than Pt/C in a system with bacteria metabolism and thus holds great potential for practical MFC applications.

  6. Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2015-11-01

    This work is focussed on the processing of cathodic active material of spent lithium ion batteries (LIBs) to ensure resource recovery and minimize environmental degradation. The sulfuric acid leaching of metals was carried out for the recovery of all the valuable metals including nickel and manganese along with the frequently targeted metals like lithium and cobalt. The process parameters such as acid concentration, pulp density, time and temperature for the leaching of metals from the cathode powder containing 35.8% Co, 6.5% Li, 11.6% Mn and 10.06% Ni, were optimized. Results show the optimized leach recovery of 93.4% Li, 66.2% Co, 96.3% Ni and 50.2% Mn when the material was leached in 1M H2SO4 at 368 K and 50 g/L pulp density for 240 min. The need of a reductant for improved recovery of cobalt and manganese has been explained by the thermodynamic analysis (Eh-pH diagram) for these metals. Leaching of the valuable metals was found to follow the logarithmic rate law controlled by surface layer diffusion of the lixiviant reacting with the particles. The mode of leaching of the metals from the spent LIBs was further examined by chemical analysis of the samples at various stage of processing which was further corroborated by characterizing the untreated sample and the leach residues by XRD phase identification and the SEM-EDS studies. PMID:26087645

  7. Electrochemical properties of large-sized pouch-type lithium ion batteries with bio-inspired organic cathode materials

    NASA Astrophysics Data System (ADS)

    Yeo, Jae-Seong; Yoo, Eun-Ji; Ha, Sang-Hyeon; Cheong, Dong-Ik; Cho, Sung-Baek

    2016-05-01

    To investigate the feasibility of scaling up bio-inspired organic materials as cathode materials in lithium ion batteries, large-sized pouch cells are successfully prepared via tape casting using lumichrome with an alloxazine structure and aqueous styrene butadiene rubber-carboxymethyl cellulose (SBR-CMC) binders. A battery module with a two-in-series, six-in-parallel (2S6P) configuration is also successfully fabricated and is able to power blue LEDs (850 mW). Lumichrome shows no structural changes during the fabrication processes used to produce the positive electrode. The large-sized pouch cells show two sets of cathodic and anodic peaks with average potentials of 2.58 V and 2.26 V vs. Li/Li+, respectively. The initial discharge capacities are 142 mAh g-1 and 148 mAh g-1 for ethylene carbonate-dimethyl carbonate (EC-DMC) and tetraethylene glycol dimethyl ether (TEGDME) electrolytes, respectively, similar to that of a coin cell (149 mAh g-1). The EC-DMC-injected pouch cells exhibit higher rate performance and cyclability than the TEGDME-injected ones. The TEGDME electrolyte is not suitable for lithium metal anodes because of electrolyte decomposition and subsequent cell swelling.

  8. The influence of reduced graphene oxide on electrical conductivity of LiFePO4-based composite as cathode material

    NASA Astrophysics Data System (ADS)

    Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin; Iskandar, Ferry

    2016-02-01

    LiFePO4 is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g-1. However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO4-based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO4-based composite by varying mass of rGO in composition. Vibration of LiFePO4-based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO4 nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO.

  9. Characterization of Cathode Materials for Rechargeable Lithium Batteries using Synchrotron Based In Situ X-ray Techniques

    SciTech Connect

    Yang, Xiao-Qing

    2007-05-23

    The emergence of portable telecommunication, computer equipment and ultimately hybrid electric vehicles has created a substantial interest in manufacturing rechargeable batteries that are less expensive, non-toxic, operate for longer time, small in size and weigh less. Li-ion batteries are taking an increasing share of the rechargeable battery market. The present commercial battery is based on a layered LiCoO{sub 2} cathode and a graphitized carbon anode. LiCoO{sub 2} is expensive but it has the advantage being easily manufactured in a reproducible manner. Other low cost layered compounds such as LiNiO{sub 2}, LiNi{sub 0.85}Co{sub 0.15}O{sub 2} or cubic spinels such as LiMn{sub 2}O{sub 4} have been considered. However, these suffer from cycle life and thermal stability problems. Recently, some battery companies have demonstrated a new concept of mixing two different types of insertion compounds to make a composite cathode, aimed at reducing cost and improving self-discharge. Reports clearly showed that this blending technique can prevent the decline in ·capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and phase transitions for these composite cathodes. Understanding the structure and structural changes of electrode materials during the electrochemical cycling is the key to develop better .lithium ion batteries. The successful commercialization of the· lithium-ion battery is mainly built on the advances in solid state chemistry of the intercalation compounds. Most of the progress in understanding the lithium ion battery materials has been obtained from x-ray diffraction studies. Up to now, most XRD studies on lithium-ion battery materials have been done ex situ. Although these ex situ XRD studies have provided important information· about the structures of battery materials, they do face three major problems. First of all, the pre-selected charge (discharge) states may

  10. Optical Actionometry Of Cathode Material Sputtered Into Plasma Phase Of Glow Discharges

    NASA Astrophysics Data System (ADS)

    Wroński, Zdzisław

    2006-01-01

    Cathode sputtering by glow discharge plasma is the effective solid etching. The emission of optical lines by plasma is a complex process depending on gas used. The peculiar processes such fast ion-sputte-red atom interaction and Penning excitation have been found to contribute much to the emission of optical lines of sputtered species. The optical actionometry of sputtered atoms is not suggested to be a useful method because of a lack of proper cross sections of the above peculiar processes. At present the computer simulation of both etching and characteristics of sputtered atoms in the plasma phase seems to be the preferential method..

  11. Nitrogen--sulfur--carbon nanocomposites and their application as cathode materials in lithium--sulfur batteries

    DOEpatents

    Dai, Sheng; Sun, Xiao-Guang; Guo, Bingkun; Wang, Xiqing; Mayes, Richard T.; Ben, Teng; Qiu, Shilun

    2016-09-27

    The invention is directed in a first aspect to electron-conducting porous compositions comprising an organic polymer matrix doped with nitrogen atoms and having elemental sulfur dispersed therein, particularly such compositions having an ordered framework structure. The invention is also directed to composites of such S/N-doped electron-conducting porous aromatic framework (PAF) compositions, or composites of an S/N-doped mesoporous carbon composition, which includes the S/N-doped composition in admixture with a binder, and optionally, conductive carbon. The invention is further directed to cathodes for a lithium-sulfur battery in which such composites are incorporated.

  12. Energetics of perovskite-type materials applied in solid oxide fuel cells (SOFCs): Electrolytes, cathodes and interconnects

    NASA Astrophysics Data System (ADS)

    Cheng, Jihong

    Perovskite-type oxides (ABO3) find a great variety of applications in solid oxide fuel cells (SOFCs), including solid electrolytes, cathodes and interconnects, which are closely related to the defect chemistry involved. Thermodynamic studies are needed to systematically understand the nature of the structure-property relations and provide guidance to predict and/or select proper materials. High temperature solution calorimetry in molten oxide solvents is a powerful tool and has been applied for several perovskite systems that have simple (undoped) and complex (doped) compositions. LaBO3 perovskites (B = Al, Ga, Sc, In, Cr, Fe, Co, Ni) represent a group of excellent parent materials for electrolytes, cathodes, and interconnects in SOFCs. Their enthalpies of formation from oxides generally exhibit a relationship between stability and the major structural parameter for perovskites, the tolerance factor. As the tolerance factor deviates more from unity, the enthalpy of formation from oxides becomes less exothermic. This work verifies this general trend for A3+B3+O3 type perovskites, joining other two types, i.e., A1+B5+O 3 and A2+B4+O3. In alkaline earth doped perovskites, though structural parameters are likely to continue affecting stability, defects, which are introduced upon doping, actually play a more profound role in defining energetic trends. In the newly developed electrolyte materials, Mg, Sr, and Ba-doped LaGaO 3 perovskites, oxygen vacancies are created to compensate the charge imbalance between dopant and host ions. Oxygen vacancies have a destabilization effect on the structure due to the partial disconnection of the corner-shared BO6 octahedral framework. On the other hand, they tend to order at the short-range scale, forming vacancy-dopant clusters, as evidenced by neutron diffraction. In alkaline earth doped perovskites that contain transition metals, two charge compensation scenarios are possible: oxidation of the transition metal or creation of

  13. Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

    PubMed

    Wang, Hong; Yang, Chi; Liu, Shu-Xin

    2014-09-01

    Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

  14. Porous LiFePO4/C microspheres as high-power cathode materials for lithium ion batteries.

    PubMed

    Sun, Bing; Wang, Ying; Wang, Bei; Kim, Hyun-Soo; Kim, Woo-Seong; Wang, Guoxiu

    2013-05-01

    Porous LiFePO4/C microspheres were synthesized by a novel hydrothermal reaction combined with high-temperature calcinations. The morphology of the prepared material was investigated by field-emission scanning electron microscopy. Porous microspheres with diameters around 1-3 microm were obtained, which consisting of primary LiFePO4 nanoparticles. The electrochemical performances of the as-prepared LiFePO4 microspheres were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge cycling. The carbon coated LiFePO4 microspheres showed lower polarization, higher rate capability, and better cycling stability than that of pristine LiFePO4 microspheres, indicating the potential application as the cathode material for high-power lithium ion batteries.

  15. A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries.

    PubMed

    Guo, Shaohua; Yu, Haijun; Jian, Zelang; Liu, Pan; Zhu, Yanbei; Guo, Xianwei; Chen, Mingwei; Ishida, Masayoshi; Zhou, Haoshen

    2014-08-01

    A layered sodium manganese oxide material (NaMn3 O5 ) is introduced as a novel cathode materials for sodium-ion batteries. Structural characterizations reveal a typical Birnessite structure with lamellar stacking of the synthetic nanosheets. Electrochemical tests reveal a particularly large discharge capacity of 219 mAh g(-1) in the voltage rang of 1.5-4.7 V vs. Na/Na(+) . With an average potential of 2.75 V versus sodium metal, layered NaMn3 O5 exhibits a high energy density of 602 Wh kg(-1) , and also presents good rate capability. Furthermore, the diffusion coefficient of sodium ions in the layered NaMn3 O5 electrode is investigated by using the galvanostatic intermittent titration technique. The results greatly contribute to the development of room-temperature sodium-ion batteries based on earth-abundant elements.

  16. Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

    NASA Astrophysics Data System (ADS)

    Crowe, Adam J.; Bartlett, Bart M.

    2016-10-01

    With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg2+), relative to lithium-ion (Li+) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg2+, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes.

  17. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials.

    PubMed

    Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander; Malik, Rahul; Kang, ShinYoung; Ceder, Gerbrand

    2016-07-01

    Lithium-ion batteries are now reaching the energy density limits set by their electrode materials, requiring new paradigms for Li(+) and electron hosting in solid-state electrodes. Reversible oxygen redox in the solid state in particular has the potential to enable high energy density as it can deliver excess capacity beyond the theoretical transition-metal redox-capacity at a high voltage. Nevertheless, the structural and chemical origin of the process is not understood, preventing the rational design of better cathode materials. Here, we demonstrate how very specific local Li-excess environments around oxygen atoms necessarily lead to labile oxygen electrons that can be more easily extracted and participate in the practical capacity of cathodes. The identification of the local structural components that create oxygen redox sets a new direction for the design of high-energy-density cathode materials. PMID:27325096

  18. Investigating the reversibility of structural modifications of LixNiyMnzCo1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

    DOE PAGES

    Hwang, Sooyeon; Bak, Seong -Min; Kim, Seung Min; Chung, Kyung Yoon; Chang, Wonyoung

    2015-08-11

    In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of LixNiyMnzCo1-y-zO₂ (NMC; y, z = 0.8, 0.1 and 0.4, 0.3, respectively) cathode materials during the initial charge/discharge. Various analytical tools, such as X-ray diffraction, selected-area electron diffraction, electron energy-loss spectroscopy, and high-resolution electron microscopy, are used to examine the structural properties of the NMC cathode materials at the three different scales. Cut-off voltages of 4.3 and 4.8 V are applied during the electrochemical tests as the normal and extreme conditions, respectively. The high-Ni-content NMC cathode materials exhibit unusual behaviors, which is deviate frommore » the general redox reactions during the charge or discharge. The transition metal (TM) ions in the high-Ni-content NMC cathode materials, which are mostly Ni ions, are reduced at 4.8 V, even though TMs are usually oxidized to maintain charge neutrality upon the removal of Li. It was found that any changes in the crystallographic and electronic structures are mostly reversible down to the sub-surface scale, despite the unexpected reduction of Ni ions. However, after the discharge, traces of the phase transitions remain at the edges of the NMC cathode materials at the scale of a few nanometers (i.e., surface scale). This study demonstrates that the structural modifications in NMC cathode materials are induced by charge as well as discharge at multiple length scales. These changes are nearly reversible after the first cycle, except at the edges of the samples, which should be avoided because these highly localized changes can initiate battery degradation.« less

  19. Cobalt based layered perovskites as cathode material for intermediate temperature Solid Oxide Fuel Cells: A brief review

    NASA Astrophysics Data System (ADS)

    Pelosato, Renato; Cordaro, Giulio; Stucchi, Davide; Cristiani, Cinzia; Dotelli, Giovanni

    2015-12-01

    Nowadays, the cathode is the most studied component in Intermediate Temperature-Solid Oxide Fuel Cells (IT-SOFCs). Decreasing SOFCs operating temperature implies slow oxygen reduction kinetics and large polarization losses. Double perovskites with general formula REBaCo2O5+δ are promising mixed ionic-electronic conductors, offering a remarkable enhancement of the oxygen diffusivity and surface exchange respect to disordered perovskites. In this review, more than 250 compositions investigated in the literature were analyzed. The evaluation was performed in terms of electrical conductivity, Area Specific Resistance (ASR), chemical compatibility with electrolytes and Thermal Expansion Coefficient (TEC). The most promising materials have been identified as those bearing the mid-sized rare earths (Pr, Nd, Sm, Gd). Doping strategies have been analyzed: Sr doping on A site promotes higher electrical conductivity, but worsen ASR and TECs; B-site doping (Fe, Ni, Mn) helps lowering TECs, but is detrimental for the electrochemical properties. A promising boost of the electrochemical activity is obtained by simply introducing a slight Ba under-stoichiometry. Still, the high sensitivity of the electrochemical properties against slight changes in the stoichiometry hamper a conclusive comparison of all the investigated compounds. Opportunities for an improvement of double perovskite cathodes performance is tentatively foreseen in combining together the diverse effective doping strategies.

  20. A preliminary investigation into the new class of lithium intercalating LiNiSiO4 cathode material

    NASA Astrophysics Data System (ADS)

    Jayaprakash, N.; Kalaiselvi, N.; Periasamy, P.

    2008-01-01

    A unique attempt to exploit silicate chemistry for a possible enhancement of the electrochemical properties of a lithium ion system via exploration of the novel category lithium intercalating LiNiSiO4 cathode has been made through the present study. A novel citric acid assisted modified sol-gel method (CAM sol-gel) has been adopted to synthesize the title compound with a formation temperature positioned well below 500 °C, as derived from thermal studies. A powder x-ray diffraction (PXRD) pattern evidenced the absence of undesirable peaks and confirmed the formation of a hexagonal lattice structure with enhanced crystallinity and phase purity, and the presence of uniformly distributed particles of ~200 nm size with well defined grain boundaries is obvious from the scanning electron microscopy (SEM) image of LiNiSiO4 material. Further, magic angle spinning (MAS) 7Li nuclear magnetic resonance (NMR) results from LiNiSiO4 confirmed the presence of a layered type of crystal arrangement. A cyclic voltammetry (CV) study performed on a LiNiSiO4 cathode revealed an excellent reversibility without any change in the peak position upon extended cycling, thus substantiating the structural stability upon progressive cycling.

  1. The synergistic effect of inert oxide and metal fluoride dual coatings on advanced cathode materials for lithium ion battery applications.

    PubMed

    Park, Kwangjin; Lee, Byoung-Sun; Park, Jun-Ho; Hong, Suk-Gi

    2016-06-21

    The effect of Al2O3/LiF dual coatings on the electrochemical performance of over-lithiated layered oxide (OLO) has been investigated. A uniform coating of Al2O3 and LiF is obtained on the surface of the layered pristine material. The OLO with a dual Al2O3/LiF coating with a ratio of 1 : 1.5 exhibits excellent electrochemical performance. An initial discharge capacity of 265.66 mA h g(-1) is obtained at a C-rate of 0.1C. This capacity is approximately 15 mA h g(-1) higher than that of pristine OLO. The capacity retention (92.8% at the 50th cycle) is also comparable to that of pristine OLO (91.4% at the 50th cycle). Coating the cathode with a dual layer comprising Al2O3 and LiF leads to improved charging and discharging kinetics, and prevents direct contact between the cathode and the electrolyte.

  2. Nonaqueous lithium-ion capacitors with high energy densities using trigol-reduced graphene oxide nanosheets as cathode-active material.

    PubMed

    Aravindan, Vanchiappan; Mhamane, Dattakumar; Ling, Wong Chui; Ogale, Satishchandra; Madhavi, Srinivasan

    2013-12-01

    One HEC of a material: The use of trigol-reduced graphene oxide nanosheets as cathode material in hybrid lithium-ion electrochemical capacitors (Li-HECs) results in an energy density of 45 Wh kg(-1) ; much enhanced when compared to similar devices. The mass loading of the active materials is optimized, and the devices show good cycling performance. Li-HECs employing these materials outperform other supercapacitors, making them attractive for use in power sources.

  3. New lithium iron pyrophosphate as 3.5 V class cathode material for lithium ion battery.

    PubMed

    Nishimura, Shin-ichi; Nakamura, Megumi; Natsui, Ryuichi; Yamada, Atsuo

    2010-10-01

    A new pyrophosphate compound Li(2)FeP(2)O(7) was synthesized by a conventional solid-state reaction, and its crystal structure was determined. Its reversible electrode operation at ca. 3.5 V vs Li was identified with the capacity of a one-electron theoretical value of 110 mAh g(-1) even for ca. 1 μm particles without any special efforts such as nanosizing or carbon coating. Li(2)FeP(2)O(7) and its derivatives should provide a new platform for related lithium battery electrode research and could be potential competitors to commercial olivine LiFePO(4), which has been recognized as the most promising positive cathode for a lithium-ion battery system for large-scale applications, such as plug-in hybrid electric vehicles.

  4. A new cathode material for super-valent battery based on aluminium ion intercalation and deintercalation

    PubMed Central

    Wang, Wei; Jiang, Bo; Xiong, Weiyi; Sun, He; Lin, Zheshuai; Hu, Liwen; Tu, Jiguo; Hou, Jungang; Zhu, Hongmin; Jiao, Shuqiang

    2013-01-01

    Due to their small footprint and flexible siting, rechargeable batteries are attractive for energy storage systems. A super-valent battery based on aluminium ion intercalation and deintercalation is proposed in this work with VO2 as cathode and high-purity Al foil as anode. First-principles calculations are also employed to theoretically investigate the crystal structure change and the insertion-extraction mechanism of Al ions in the super-valent battery. Long cycle life, low cost and good capacity are achieved in this battery system. At the current density of 50 mAg−1, the discharge capacity remains 116 mAhg−1 after 100 cycles. Comparing to monovalent Li-ion battery, the super-valent battery has the potential to deliver more charges and gain higher specific capacity. PMID:24287676

  5. A new cathode material for super-valent battery based on aluminium ion intercalation and deintercalation.

    PubMed

    Wang, Wei; Jiang, Bo; Xiong, Weiyi; Sun, He; Lin, Zheshuai; Hu, Liwen; Tu, Jiguo; Hou, Jungang; Zhu, Hongmin; Jiao, Shuqiang

    2013-11-29

    Due to their small footprint and flexible siting, rechargeable batteries are attractive for energy storage systems. A super-valent battery based on aluminium ion intercalation and deintercalation is proposed in this work with VO2 as cathode and high-purity Al foil as anode. First-principles calculations are also employed to theoretically investigate the crystal structure change and the insertion-extraction mechanism of Al ions in the super-valent battery. Long cycle life, low cost and good capacity are achieved in this battery system. At the current density of 50 mAg(-1), the discharge capacity remains 116 mAhg(-1) after 100 cycles. Comparing to monovalent Li-ion battery, the super-valent battery has the potential to deliver more charges and gain higher specific capacity.

  6. Y-doped Li8ZrO6: A Li-Ion Battery Cathode Material with High Capacity.

    PubMed

    Huang, Shuping; Wilson, Benjamin E; Wang, Bo; Fang, Yuan; Buffington, Keegan; Stein, Andreas; Truhlar, Donald G

    2015-09-01

    We study--experimentally and theoretically--the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li8ZrO6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li(+) for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/discharge cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO2, and O2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li6ZrO6 and Li5ZrO6 delithiation products can be thermodynamically metastable to release of O2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole. PMID:26264394

  7. Cathodes - Technological review

    SciTech Connect

    Cherkouk, Charaf; Nestler, Tina

    2014-06-16

    Lithium cobalt oxide (LiCoO{sub 2}) was already used in the first commercialized Li-ion battery by SONY in 1990. Still, it is the most frequently used cathode material nowadays. However, LiCoO{sub 2} is intrinsically unstable in the charged state, especially at elevated temperatures and in the overcharged state causing volume changes and transport limitation for high power batteries. In this paper, some technological aspects with large impact on cell performance from the cathode material point of view will be reviewed. At first it will be focused on the degradation processes and life-time mechanisms of the cathode material LiCoO{sub 2}. Electrochemical and structural results on commercial Li-ion batteries recorded during the cycling will be discussed. Thereafter, advanced nanomaterials for new cathode materials will be presented.

  8. Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries.

    PubMed

    Shi, Ji-Lei; Zhang, Jie-Nan; He, Min; Zhang, Xu-Dong; Yin, Ya-Xia; Li, Hong; Guo, Yu-Guo; Gu, Lin; Wan, Li-Jun

    2016-08-10

    Li-rich layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, they suffer from severe voltage decay upon cycling, which hinders their further commercialization. Here, we report a Li-rich layered material 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 with high nickel content, which exhibits much slower voltage decay during long-term cycling compared to conventional Li-rich materials. The voltage decay after 200 cycles is 201 mV. Combining in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, and scanning transmission electron microscopy, we demonstrate that nickel ions act as stabilizing ions to inhibit the Jahn-Teller effect of active Mn(3+) ions, improving d-p hybridization and supporting the layered structure as a pillar. In addition, nickel ions can migrate between the transition-metal layer and the interlayer, thus avoiding the formation of spinel-like structures and consequently mitigating the voltage decay. Our results provide a simple and effective avenue for developing Li-rich layered materials with mitigated voltage decay and a long lifespan, thereby promoting their further application in lithium-ion batteries with high energy density. PMID:27437556

  9. Functioning mechanism of AlF3 coating on the Li- and Mn-rich cathode materials

    SciTech Connect

    Zheng, Jianming; Gu, Meng; Xiao, Jie; Polzin, Bryant; Yan, Pengfei; Chen, Xilin; Wang, Chong M.; Zhang, Jiguang

    2014-11-25

    Li- and Mn-rich (LMR) material is a very promising cathode for lithium ion batteries because of their high theoretical energy density (~900 Wh kg-1) and low cost. However, their poor long-term cycling stability, voltage fade, and low rate capability are significant barriers hindered their practical applications. Surface coating, e.g. AlF3 coating, can significantly improve the capacity retention and enhance the rate capability. However, the fundamental mechanism of this improvement and the microstructural evolution related to the surface coating is still not well understood. Here, we report systematic studies of the microstructural changes of uncoated and AlF3-coated materials before and after cycling using aberration-corrected scanning/transmission electron microscopy and electron energy loss spectroscopy. The results reveal that surface coating can reduce the oxidation of electrolyte at high voltage, thus suppressing the accumulation of SEI layer on electrode particle surface. Surface coating also enhances structural stability of the surface region (especially the electrochemically transformed spinel-like phase), and protects the electrode from severe etching/corrosion by the acidic species in the electrolyte, therefore limiting the degradation of the material. Moreover, surface coating can alleviate the undesirable voltage fade by minimize layered-spinel phase transformation in the bulk region of the materials. These fundamental findings may also be widely applied to explain the functioning mechanism of other surface coatings used in a broad range of electrode materials.

  10. Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries.

    PubMed

    Shi, Ji-Lei; Zhang, Jie-Nan; He, Min; Zhang, Xu-Dong; Yin, Ya-Xia; Li, Hong; Guo, Yu-Guo; Gu, Lin; Wan, Li-Jun

    2016-08-10

    Li-rich layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, they suffer from severe voltage decay upon cycling, which hinders their further commercialization. Here, we report a Li-rich layered material 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 with high nickel content, which exhibits much slower voltage decay during long-term cycling compared to conventional Li-rich materials. The voltage decay after 200 cycles is 201 mV. Combining in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, and scanning transmission electron microscopy, we demonstrate that nickel ions act as stabilizing ions to inhibit the Jahn-Teller effect of active Mn(3+) ions, improving d-p hybridization and supporting the layered structure as a pillar. In addition, nickel ions can migrate between the transition-metal layer and the interlayer, thus avoiding the formation of spinel-like structures and consequently mitigating the voltage decay. Our results provide a simple and effective avenue for developing Li-rich layered materials with mitigated voltage decay and a long lifespan, thereby promoting their further application in lithium-ion batteries with high energy density.

  11. Cu doped V2O5 flowers as cathode material for high-performance lithium ion batteries.

    PubMed

    Yu, Hong; Rui, Xianhong; Tan, Huiteng; Chen, Jing; Huang, Xin; Xu, Chen; Liu, Weiling; Yu, Denis Y W; Hng, Huey Hoon; Hoster, Harry E; Yan, Qingyu

    2013-06-01

    Hierarchical Cu doped vanadium pentoxide (V2O5) flowers were prepared via a simple hydrothermal approach followed by an annealing process. The flower precursors are self-assembled with 1D nanobelts surrounding a central core. The morphological evolution is investigated and a plausible mechanism is proposed. As the cathode material for lithium ion batteries, the Cu doped V2O5 samples exhibit improved electrochemical performance compared to the un-doped ones. Among them Cu0.02V1.98O5 delivered higher reversible specific capacities, better cycling stabilities and excellent rate capabilities, e.g. 97 mA h g(-1) at 20.0 C.

  12. Facile molten salt synthesis of Li2NiTiO4 cathode material for Li-ion batteries.

    PubMed

    Wang, Yanming; Wang, Yajing; Wang, Fei

    2014-01-01

    Well-crystallized Li2NiTiO4 nanoparticles are rapidly synthesized by a molten salt method using a mixture of NaCl and KCl salts. X-ray diffraction pattern and scanning electron microscopic image show that Li2NiTiO4 has a cubic rock salt structure with an average particle size of ca. 50 nm. Conductive carbon-coated Li2NiTiO4 is obtained by a facile ball milling method. As a novel 4 V positive cathode material for Li-ion batteries, the Li2NiTiO4/C delivers high discharge capacities of 115 mAh g(-1) at room temperature and 138 mAh g(-1) and 50°C, along with a superior cyclability. PMID:24855459

  13. Understanding Voltage Decay in Lithium-Rich Manganese-Based Layered Cathode Materials by Limiting Cutoff Voltage.

    PubMed

    Yang, Jingsong; Xiao, Lifen; He, Wei; Fan, Jiangwei; Chen, Zhongxue; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2016-07-27

    The effect of the cutoff voltages on the working voltage decay and cyclability of the lithium-rich manganese-based layered cathode (LRMO) was investigated by electrochemical measurements, electrochemical impedance spectroscopy, ex situ X-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy line scan technologies. It was found that both lower (2.0 V) and upper (4.8 V) cutoff voltages cause severe voltage decay with cycling due to formation of the spinel phase and migration of the transition metals inside the particles. Appropriate cutoff voltage between 2.8 and 4.4 V can effectively inhibit structural variation as the electrode demonstrates 92% capacity retention and indiscernible working voltage decay over 430 cycles. The results also show that phase transformation not only on high charge voltage but also on low discharge voltage should be addressed to obtain highly stable LRMO materials. PMID:27383918

  14. Study of the Durability of Doped Lanthanum Manganite and Cobaltite Cathode Materials under ''Real World'' Air Exposure Atmospheres

    SciTech Connect

    Singh, Prabhakar; Mahapatra, Manoj; Ramprasad, Rampi; Minh, Nguyen; Misture, Scott

    2014-11-30

    The overall objective of the program is to develop and validate mechanisms responsible for the overall structural and chemical degradation of lanthanum manganite as well as lanthanum ferrite cobaltite based cathode when exposed to “real world” air atmosphere exposure conditions during SOFC systems operation. Of particular interest are the evaluation and analysis of degradation phenomena related to and responsible for (a) products formation and interactions with air contaminants, (b) dopant segregation and oxide exolution at free surfaces, (c) cation interdiffusion and reaction products formation at the buried interfaces, (d) interface morphology changes, lattice transformation and the development of interfacial porosity and (e) micro-cracking and delamination from the stack repeat units. Reaction processes have been studied using electrochemical and high temperature materials compatibility tests followed by structural and chemical characterization. Degradation hypothesis has been proposed and validated through further experimentation and computational simulation.

  15. Facile molten salt synthesis of Li2NiTiO4 cathode material for Li-ion batteries.

    PubMed

    Wang, Yanming; Wang, Yajing; Wang, Fei

    2014-01-01

    Well-crystallized Li2NiTiO4 nanoparticles are rapidly synthesized by a molten salt method using a mixture of NaCl and KCl salts. X-ray diffraction pattern and scanning electron microscopic image show that Li2NiTiO4 has a cubic rock salt structure with an average particle size of ca. 50 nm. Conductive carbon-coated Li2NiTiO4 is obtained by a facile ball milling method. As a novel 4 V positive cathode material for Li-ion batteries, the Li2NiTiO4/C delivers high discharge capacities of 115 mAh g(-1) at room temperature and 138 mAh g(-1) and 50°C, along with a superior cyclability.

  16. Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials

    SciTech Connect

    Yan, Pengfei; Zheng, Jianming; Lv, Dongping; Wei, Yi; Zheng, Jiaxin; Wang, Zhiguo; Kuppan, Saravanan; Yu, Jianguo; Luo, Langli; Edwards, Danny J.; Olszta, Matthew J.; Amine, Khalil; Liu, Jun; Xiao, Jie; Pan, Feng; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

    2015-07-06

    Capacity and voltage fading of layer structured cathode based on lithium transition metal oxide is closely related to the lattice position and migration behavior of the transition metal ions. However, it is scarcely clear about the behavior of each of these transition metal ions. We report direct atomic resolution visualization of interatomic layer mixing of transition metal (Ni, Co, Mn) and lithium ions in layer structured oxide cathodes for lithium ion batteries. Using chemical imaging with aberration corrected scanning transmission electron microscope (STEM) and DFT calculations, we discovered that in the layered cathodes, Mn and Co tend to reside almost exclusively at the lattice site of transition metal (TM) layer in the structure or little interlayer mixing with Li. In contrast, Ni shows high degree of interlayer mixing with Li. The fraction of Ni ions reside in the Li layer followed a near linear dependence on total Ni concentration before reaching saturation. The observed distinctively different behavior of Ni with respect to Co and Mn provides new insights on both capacity and voltage fade in this class of cathode materials based on lithium and TM oxides, therefore providing scientific basis for selective tailoring of oxide cathode materials for enhanced performance.

  17. Preliminary studies of biominerals-coated spinel LiMn2 O4 as a cathode material on electrochemical performances for Li-ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Vediappan, Kumaran; Lee, Chang Woo

    2010-05-01

    Lithium manganese oxide (LiMn2O4) is an inexpensive and pollution-free cathode material for Li-ion rechargeable batteries. In this study, spinel LiMn2O4 cathode material was coated with biomineral powders by the mechano-chemical method. In the course of the material synthesis, citric acid and acryl amide were added to serve as a complexing agent and a gelling agent, respectively, followed by a calcination process at 700 °C for 6 h in a high-purity argon atmosphere. The spinel LiMn2O4 and biominerals-coated spinel LiMn2O4 cathode materials were, from diverse viewpoints, characterized by x-ray diffraction, field emission-scanning electron microscopy, Fourier transform infrared spectroscopy and the electrochemical cycling method to understand the mechanism of improvements in electrochemical performances. We suggest that the biominerals-coated spinel LiMn2O4 is a good candidate as a low cost and environmentally friendly cathode material showing the enlarged capacity characteristic of Li-ion rechargeable batteries.

  18. Electrolytic Reduction of Spent Nuclear Oxide Fuel -- Effects of Fuel Form and Cathode Containment Materials on Bench-Scale Operations

    SciTech Connect

    S. D. Herrmann

    2007-09-01

    A collaborative effort between the Idaho National Laboratory (INL) and Korea Atomic Energy Research Institute (KAERI) is underway per an International Nuclear Energy Research Initiative to advance the development of a pyrochemical process for the treatment of spent nuclear oxide fuel. To assess the effects of specific process parameters that differ between oxide reduction operations at INL and KAERI, a series of 4 electrolytic reduction runs will be performed with a single salt loading of LiCl-Li2O at 650 °C using a test apparatus located inside of a hot cell at INL. The spent oxide fuel for the tests will be irradiated UO2 that has been subjected to a voloxidation process to form U3O8. The primary variables in the 4 electrolytic reduction runs will be fuel basket containment material and Li2O concentration in the LiCl salt. All 4 runs will be performed with comparable fuel loadings (approximately 50 g) and fuel compositions and will utilize a platinum anode and a Ni/NiO reference electrode. The first 2 runs will elucidate the effect of fuel form on the electrolytic reduction process by comparison of the above test results with U3O8 versus results from previous tests with UO2. The first 3 runs will investigate the impact that the cathode containment material has on the electrolytic reduction of spent oxide fuel. The 3rd and 4th runs will investigate the effect of Li2O concentration on the reduction process with a porous MgO cathode containment.

  19. First principle study of LiXS2 (X = Ga, In) as cathode materials for Li ion batteries

    NASA Astrophysics Data System (ADS)

    Feng-Ya, Rao; Fang-Hua, Ning; Li-Wei, Jiang; Xiang-Ming, Zeng; Mu-Sheng, Wu; Bo, Xu; Chu-Ying, Ouyang

    2016-02-01

    From first principle calculations, we demonstrate that LiXS2 (X = Ga, In) compounds have potential applications as cathode materials for Li ion batteries. It is shown that Li can be extracted from the LiXS2 lattice with relatively small volume change and the XS4 tetrahedron structure framework remains stable upon delithiation. The theoretical capacity and average intercalation potential of the LiGaS2 (LiInS2) cathode are 190.4 (144.2) mAh/g and 3.50 V (3.53 V). The electronic structures of the LiXS2 are insulating with band gaps of 2.88 eV and 1.99 eV for X = Ga and In, respectively. However, Li vacancies, which are formed through delithiation, change the electronic structure substantially from insulating to metallic structure, indicating that the electrical conductivities of the LiXS2 compounds should be good during cycling. Li ion migration energy barriers are also calculated, and the results show that Li ion diffusions in the LiXS2 compounds can be as good as those in the currently widely used electrode materials. Project supported by the National High Technology and Development Key Program, China (Grant No. 2015AA034201), the National Natural Science Foundation of China (Grant Nos. 11234013 and 11264014), the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20133ACB21010, 20142BAB212002, and 20132BAB212005), and the Foundation of Jiangxi Provincial Education Committee, China (Grant Nos. GJJ14254 and KJLD14024).

  20. Hydrogen hollow cathode ion source

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J., Jr.; Sovey, J. S.; Roman, R. F. (Inventor)

    1980-01-01

    A source of hydrogen ions is disclosed and includes a chamber having at one end a cathode which provides electrons and through which hydrogen gas flows into the chamber. Screen and accelerator grids are provided at the other end of the chamber. A baffle plate is disposed between the cathode and the grids and a cylindrical baffle is disposed coaxially with the cathode at the one end of the chamber. The cylindrical baffle is of greater diameter than the baffle plate to provide discharge impedance and also to protect the cathode from ion flux. An anode electrode draws the electrons away from the cathode. The hollow cathode includes a tubular insert of tungsten impregnated with a low work function material to provide ample electrons. A heater is provided around the hollow cathode to initiate electron emission from the low work function material.

  1. Preparation of Nanocomposite GDC/LSCF Cathode Material for IT-SOFC by Induction Plasma Spraying

    NASA Astrophysics Data System (ADS)

    Shen, Yan; Almeida, Veronica Alexandra B.; Gitzhofer, François

    2011-01-01

    Homogeneous mixtures of Ce0.8Gd0.2O1.9 (GDC) and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) nanopowders were successfully synthesized using induction plasma by axial injection of a solution. The resulting nanocomposite powders consisted of two kinds of nanopowders with different mass ratio of GDC/LSCF, such as 3/7 and 6/4. The morphological features, crystallinity, and the phases of the synthesized powders were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), local energy-dispersive x-ray spectroscopy (EDS) analysis, and x-ray diffraction (XRD). The nanopowders are almost globular in shape with a diameter smaller than 100 nm and their BET specific areas are around 20 m2 g-1. The GDC and LSCF phases are well distributed in the nanopowders. In addition, suspensions, made with the as-synthesized composite nanopowders and ethanol, were used to deposit cathode coatings using suspension plasma spray (SPS). Micro-nanostructures of the coatings are discussed. The coatings are homogeneous and porous (51% porosity) with cauliflower structures.

  2. Fe-Si networks in Na2FeSiO4 cathode materials.

    PubMed

    Wu, P; Wu, S Q; Lv, X; Zhao, X; Ye, Z; Lin, Z; Wang, C Z; Ho, K M

    2016-08-24

    Using a combination of adaptive genetic algorithm search, motif-network search scheme and first-principles calculations, we have systematically studied the low-energy crystal structures of Na2FeSiO4. We show that the low-energy crystal structures with different space group symmetries can be classified into several families based on the topologies of their Fe-Si networks. In addition to the diamond-like network which is shared by most of the low-energy structures, another three robust Fe-Si networks are also found to be stable during the charge/discharge process. The electrochemical properties of representative structures from these four different Fe-Si networks in Na2FeSiO4 and Li2FeSiO4 are investigated and found to be strongly correlated with the Fe-Si network topologies. Our studies provide a new route to characterize the crystal structures of Na2FeSiO4 and Li2FeSiO4 and offer useful guidance for the design of promising cathodes for Na/Li ion batteries. PMID:27523264

  3. Evaluation of wear rates and mechanisms of titanium diboride-graphite composite materials proposed for use as cathodes in Hall-Heroult cells

    SciTech Connect

    Pool, K.H.; Brimhall, J.L.; Raney, P.J.; Hart, P.E.

    1987-01-01

    Purpose of this study was to measure the initial wear rates of TiB/sub 2/ carbon-containing cathode materials (TiB/sub 2/-G) under electrolytic conditions. Parameters evaluated included bath ratio, current density, and aluminum pad thickness. In order to measure initial wear rates, the tests were limited to 8 h.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    PubMed

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

    2016-02-10

    The Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2 cathode material is modified by a Li4M5O12-like heterostructure and a BiOF surface layer. The interfacial heterostructure triggers the layered-to-Li4M5O12 transformation of the material which is different from the layered-to-LiMn2O4 transformation of the pristine Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. This Li4M5O12-like transformation helps the material to keep high working voltage, long cycle life and excellent rate capability. Mass spectrometry, in situ X-ray diffraction and transmission electron microscope show that the Li4M5O12-like phase prohibits oxygen release from the material bulk at elevated temperatures. In addition, the BiOF coating layer protects the material from harmful side reactions with the electrolyte. These advantages significantly improve the electrochemical performance of Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. The material shows a discharge capacity of 292 mAh g(-1) at 0.2 C with capacity retention of 92% after 100 cycles. Moreover, a high discharge capacity of 78 mAh g(-1) could be obtained at 25 C. The exothermic temperature of the fully charged electrode is elevated from 203 to 261 °C with 50% reduction of the total thermal release, highlighting excellent thermal safety of the material. PMID:26799857

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

    PubMed

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

    2016-02-10

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

  7. Miniaturized cathodic arc plasma source

    DOEpatents

    Anders, Andre; MacGill, Robert A.

    2003-04-15

    A cathodic arc plasma source has an anode formed of a plurality of spaced baffles which extend beyond the active cathode surface of the cathode. With the open baffle structure of the anode, most macroparticles pass through the gaps between the baffles and reflect off the baffles out of the plasma stream that enters a filter. Thus the anode not only has an electrical function but serves as a prefilter. The cathode has a small diameter, e.g. a rod of about 1/4 inch (6.25 mm) diameter. Thus the plasma source output is well localized, even with cathode spot movement which is limited in area, so that it effectively couples into a miniaturized filter. With a small area cathode, the material eroded from the cathode needs to be replaced to maintain plasma production. Therefore, the source includes a cathode advancement or feed mechanism coupled to cathode rod. The cathode also requires a cooling mechanism. The movable cathode rod is housed in a cooled metal shield or tube which serves as both a current conductor, thus reducing ohmic heat produced in the cathode, and as the heat sink for heat generated at or near the cathode. Cooling of the cathode housing tube is done by contact with coolant at a place remote from the active cathode surface. The source is operated in pulsed mode at relatively high currents, about 1 kA. The high arc current can also be used to operate the magnetic filter. A cathodic arc plasma deposition system using this source can be used for the deposition of ultrathin amorphous hard carbon (a-C) films for the magnetic storage industry.

  8. Enhancing the plasma illumination behaviour of microplasma devices using microcrystalline/ultra-nanocrystalline hybrid diamond materials as cathodes.

    PubMed

    Chang, Tinghsun; Lou, Shiucheng; Chen, Huangchin; Chen, Chulung; Lee, Chiyoung; Tai, Nyanhwa; Lin, Inan

    2013-08-21

    The properties of capacity-type microplasma devices were significantly enhanced due to the utilisation of hybrid diamond films as cathodes. The performance of the microplasma devices was closely correlated with the electron field emission (EFE) properties of the diamond cathode materials. The nanoemitters, which were prepared by growing duplex-structured diamond films [microcrystalline diamond (MCD)/ultra-nanocrystalline diamond (UNCD)] on Si-pyramid templates via a two-step microwave plasma enhanced chemical vapour deposition (MPE-CVD) process, exhibited improved EFE properties (E0 = 5.99 V μm(-1), J(e) = 1.10 mA cm(-2) at 8.50 V μm(-1) applied field), resulting in superior microplasma device performance (with a lower threshold field of 200 V mm(-1) and a higher plasma current density of 7.80 mA cm(-2)) in comparison with UNCD film devices prepared using a single-step MPE-CVD process. The superior EFE properties of the duplex-structured MCD-UNCD films relative to those of the UNCD films can be attributed to the unique granular structure of the diamond films. High-resolution transmission electron microscopy reveals that the MCD-UNCD films consisted of abundant graphitic phases located at the periphery of large diamond aggregates and at the boundaries between the ultra-small diamond grains. The presence of the graphite phase is presumed to be the prime factor that renders these films more conductive and causes these films to exhibit higher EFE properties, thus resulting in the improved plasma illumination properties of the microplasma devices.

  9. Mechanistic insights for the development of Li-O2 battery materials: addressing Li2O2 conductivity limitations and electrolyte and cathode instabilities.

    PubMed

    McCloskey, Bryan D; Burke, Colin M; Nichols, Jessica E; Renfrew, Sara E

    2015-08-18

    The Li-air battery has received significant attention over the past decade given its high theoretical specific energy compared to competing energy storage technologies. Yet, numerous scientific challenges remain unsolved in the pursuit of attaining a battery with modest Coulombic efficiency and high capacity. In this Feature Article, we provide our current perspective on challenges facing the development of nonaqueous Li-O2 battery cathodes. We initially present a review on our understanding of electrochemical processes occurring at the nonaqueous Li-O2 cathode. Electrolyte and cathode instabilities and Li2O2 conductivity limitations are then discussed, and suggestions for future materials research development to alleviate these issues are provided. PMID:26179598

  10. Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale

    DOE PAGES

    Wu, Yan; Ma, Cheng; Yang, Jihui; Li, Zicheng; Allard, Jr., Lawrence Frederick; Liang, Chengdu; Chi, Miaofang

    2015-01-01

    Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 tomore » 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.« less

  11. Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale

    SciTech Connect

    Wu, Yan; Ma, Cheng; Yang, Jihui; Li, Zicheng; Allard, Jr., Lawrence Frederick; Liang, Chengdu; Chi, Miaofang

    2015-01-01

    Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. However, their application is limited by the voltage decay upon cycling, and the origin of such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. Thus, this discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.

  12. Carbon Quantum Dot Surface-Engineered VO2 Interwoven Nanowires: A Flexible Cathode Material for Lithium and Sodium Ion Batteries.

    PubMed

    Balogun, Muhammad-Sadeeq; Luo, Yang; Lyu, Feiyi; Wang, Fuxin; Yang, Hao; Li, Haibo; Liang, Chaolun; Huang, Miao; Huang, Yongchao; Tong, Yexiang

    2016-04-20

    The use of electrode materials in their powdery form requires binders and conductive additives for the fabrication of the cells, which leads to unsatisfactory energy storage performance. Recently, a new strategy to design flexible, binder-, and additive-free three-dimensional electrodes with nanoscale surface engineering has been exploited in boosting the storage performance of electrode materials. In this paper, we design a new type of free-standing carbon quantum dot coated VO2 interwoven nanowires through a simple fabrication process and demonstrate its potential to be used as cathode material for lithium and sodium ion batteries. The versatile carbon quantum dots that are vastly flexible for surface engineering serve the function of protecting the nanowire surface and play an important role in the diffusion of electrons. Also, the three-dimensional carbon cloth coated with VO2 interwoven nanowires assisted in the diffusion of ions through the inner and the outer surface. With this unique architecture, the carbon quantum dot nanosurface engineered VO2 electrode exhibited capacities of 420 and 328 mAh g(-1) at current density rate of 0.3 C for lithium and sodium storage, respectively. This work serves as a milestone for the potential replacement of lithium ion batteries and next generation postbatteries.

  13. Structural and electrochemical characterization of Li{sub 2}MnSiO{sub 4} cathode material.

    SciTech Connect

    Belharouak, I.; Abouimrane, A.; Amine, K.; Chemical Sciences and Engineering Division

    2009-01-01

    The candidate cathode material Li{sub 2}MnSiO{sub 4} for lithium-ion cells was synthesized by an all-acetate precursor sol/gel method under a reducing atmosphere at 600, 700, and 800 C. The material prepared at 700 C was a pure phase and had the structural order of Li{sub 3}PO{sub 4} orthorhombic (S.G. Pmn2{sub 1}) phase. The temperature dependence of the molar magnetic susceptibility of Li{sub 2}MnSiO{sub 4} was found to be consistent with an antiferromagnetic material with a Nel temperature of 12 K. The calculated effective moment confirmed that the observed magnetic behavior involves Mn{sup 2+} ions in a high spin configuration in tetrahedral sites. Scanning electron microscopy of Li{sub 2}MnSiO{sub 4} showed large aggregates (10 to 50 {micro}m) composed of nanosized particles (100-200 nm). The as-prepared material was almost electrochemically inactive despite the presence of 15 wt % carbon additive. The material was treated by carbon coating using cellulose carbon source precursor and particle size reduction using high-energy ball milling. In coin-cell tests, the carbon-coated and ball-milled materials yielded charge capacities of 190 and 172 mAh/g, respectively, under a current density of 10 mA/g. At present, the cationic mixing between Li{sup +} and Mn{sup 2+} ions in their mutual crystallographic sites is the main impediment to the achievement of the full theoretical capacity of Li{sub 2}MnSiO{sub 4} (333 mAh/g).

  14. A novel surface-sensitive X-ray absorption spectroscopic detector to study the thermal decomposition of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Nonaka, Takamasa; Okuda, Chikaaki; Oka, Hideaki; Nishimura, Yusaku F.; Makimura, Yoshinari; Kondo, Yasuhito; Dohmae, Kazuhiko; Takeuchi, Yoji

    2016-09-01

    A surface-sensitive conversion-electron-yield X-ray absorption fine structure (CEY-XAFS) detector that operates at elevated temperatures is developed to investigate the thermal decomposition of cathode materials for Li-ion batteries. The detector enables measurements with the sample temperature controlled from room temperature up to 450 °C. The detector is applied to the LiNi0.75Co0.15Al0.05Mg0.05O2 cathode material at 0% state of charge (SOC) and 50% SOC to examine the chemical changes that occur during heating in the absence of an electrolyte. The combination of surface-sensitive CEY-XAFS and bulk-sensitive transmission-mode XAFS shows that the reduction of Ni and Co ions begins at the surface of the cathode particles at around 150 °C, and propagates inside the particle upon further heating. These changes with heating are irreversible and are more obvious at 50% SOC than at 0% SOC. The fraction of reduced Ni ions is larger than that of reduced Co ions. These results demonstrate the capability of the developed detector to obtain important information for the safe employment of this cathode material in Li-ion batteries.

  15. Na0.282V2O5: A high-performance cathode material for rechargeable lithium batteries and sodium batteries

    NASA Astrophysics Data System (ADS)

    Cai, Yangsheng; Zhou, Jiang; Fang, Guozhao; Cai, Gemei; Pan, Anqiang; Liang, Shuquan

    2016-10-01

    Na0.282V2O5 nanorods have been successfully prepared using a facile hydrothermal reaction followed by a calcination treatment, which is then used as a cathode for lithium batteries and sodium batteries for the first time. The crystal structure is refined to be a monoclinic lattice, which contains 3D tunnels along the b-axis. The Na ions are located inside the tunnels and form "pillar effect" to prevent the collapse of the crystal structure. As cathode material for lithium batteries, the Na0.282V2O5 nanorods deliver a high discharge specific capacity of 264, 186, 191 and 149 mA h g-1 at the current density of 50, 500, 1000 and 1500 mA g-1, respectively. The Na0.282V2O5 nanorods demonstrate the excellent cycling performance up to 400 cycles at 1 and 1.5 A g-1. Importantly, as cathode material for sodium batteries, Na0.282V2O5 exhibits superior long-term cyclic stability up to 1000 cycles at 0.3 A g-1. The results of ex-situ XRD, EIS and first-principle calculation indicate that the Na0.282V2O5 possesses good electrical conductivity and structural stability. Our work demonstrates that the Na0.282V2O5 material could be considered as a potential cathode for lithium-ion batteries, and even sodium ion batteries.

  16. Hollow Cathode With Multiple Radial Orifices

    NASA Technical Reports Server (NTRS)

    Brophy, John R.

    1992-01-01

    Improved hollow cathode serving as source of electrons has multiple radial orifices instead of single axial orifice. Distributes ion current more smoothly, over larger area. Prototype of high-current cathodes for ion engines in spacecraft. On Earth, cathodes used in large-diameter ion sources for industrial processing of materials. Radial orientation of orifices in new design causes current to be dispersed radially in vicinity of cathode. Advantageous where desireable to produce plasma more nearly uniform over wider region around cathode.

  17. Layered-Layered-Spinel Cathode Materials Prepared by a High-Energy Ball-Milling Process for Lithium-ion Batteries.

    PubMed

    Kim, Soo; Noh, Jae-Kyo; Aykol, Muratahan; Lu, Zhi; Kim, Haesik; Choi, Wonchang; Kim, Chunjoong; Chung, Kyung Yoon; Wolverton, Chris; Cho, Byung-Won

    2016-01-13

    In this work, we report the electrochemical properties of 0.5Li2MnO3·0.25LiNi0.5Co0.2Mn0.3O2·0.25LiNi0.5Mn1.5O4 and 0.333Li2MnO3·0.333LiNi0.5Co0.2Mn0.3O2·0.333LiNi0.5Mn1.5O4 layered-layered-spinel (L*LS) cathode materials prepared by a high-energy ball-milling process. Our L*LS cathode materials can deliver a large and stable capacity of ∼200 mAh g(-1) at high voltages up to 4.9 V, and do not show the anomalous capacity increase upon cycling observed in previously reported three-component cathode materials synthesized with different routes. Furthermore, we have performed synchrotron-based in situ X-ray diffraction measurements and found that there are no significant structural distortions during charge/discharge runs. Lastly, we carry out (opt-type) van der Waals-corrected density functional theory (DFT) calculations to explain the enhanced cycle characteristics and reduced phase transformations in our ball-milled L*LS cathode materials. Our simple synthesis method brings a new perspective on the use of the high-power L*LS cathodes in practical devices.

  18. MxMn8O16 (M = Ag or K) as promising cathode materials for secondary Mg based batteries: The role of the cation M

    DOE PAGES

    Huang, Jianping; Takeuchi, Esther S.; Altug S. Poyraz; Takeuchi, Kenneth J.; Marschilok, Amy C.

    2016-02-15

    Here, AgxMn8O16 (Ag-OMS-2) and KxMn8O16 (K-OMS-2) were investigated as high voltage cathode materials for Mg based batteries. Both MxMn8O16 materials delivered high initial capacities (>180 mA h g–1), and KxMn8O16 showed high cycle stability with a reversible capacity of >170 mA h g–1 after 20 cycles.

  19. Nb doped TiO2 as a Cathode Catalyst Support Material for Polymer Electrolyte Membrane Fuel Cells

    NASA Astrophysics Data System (ADS)

    O'Toole, Alexander W.

    In order to reduce the emissions of greenhouse gases and reduce dependence on the use of fossil fuels, it is necessary to pursue alternative sources of energy. Transportation is a major contributor to the emission of greenhouse gases due to the use of fossil fuels in the internal combustion engine. To reduce emission of these pollutants into the atmosphere, research is needed to produce alternative solutions for vehicle transportation. Low temperature polymer electrolyte membrane fuel cells are energy conversion devices that provide an alternative to the internal combustion engine, however, they still have obstacles to overcome to achieve large scale implementation. T he following work presents original research with regards to the development of Nb doped TiO2 as a cathode catalyst support material for low temperature polymer electrolyte membrane fuel cells. The development of a new process to synthesize nanoparticles of Nb doped TiO2 with controlled compositions is presented as well as methods to scale up the process and optimize the synthesis for the aforementioned application. In addition to this, comparison of both electrochemical activity and durability with current state of the art Pt on high surface area carbon black (Vulcan XC-72) is investigated. Effects of the strong metal-support interaction on the electrochemical behavior of these materials is also observed and discussed.

  20. Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

    PubMed Central

    Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

    2014-01-01

    As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries. PMID:24710575

  1. Aspergillus flavus Conidia-derived Carbon/Sulfur Composite as a Cathode Material for High Performance Lithium–Sulfur Battery

    PubMed Central

    Xu, Maowen; Jia, Min; Mao, Cuiping; Liu, Sangui; Bao, Shujuan; Jiang, Jian; Liu, Yang; Lu, Zhisong

    2016-01-01

    A novel approach was developed to prepare porous carbon materials with an extremely high surface area of 2459.6 m2g−1 by using Aspergillus flavus conidia as precursors. The porous carbon serves as a superior cathode material to anchor sulfur due to its uniform and tortuous morphology, enabling high capacity and good cycle lifetime in lithium sulfur-batteries. Under a current rate of 0.2 C, the carbon-sulfur composites with 56.7 wt% sulfur loading deliver an initial capacity of 1625 mAh g−1, which is almost equal to the theoretical capacity of sulfur. The good performance may be ascribed to excellent electronic networks constructed by the high-surface-area carbon species. Moreover, the semi-closed architecture of derived carbons can effectively retard the polysulfides dissolution during charge/discharge, resulting in a capacity of 940 mAh g−1 after 120 charge/discharge cycles. PMID:26732547

  2. Hierarchical LiNixCoyO2 mesostructures as high-performance cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Shang, Longmei; Li, He; Lai, Hongwei; Li, Danqin; Wu, Qiang; Yang, Lijun; Wang, Xizhang; Hu, Zheng

    2016-09-01

    Lithium ion batteries (LIBs) with enhanced performance to commercial ones are urgently demanded in portable electric devices. Herein, we demonstrate an efficient strategy to improve the electrochemical performance of a dominant commercial cathode material (LiCoO2) by constructing 3D hierarchical LiNixCoyO2 (h-LNCO). The h-LNCO presents porous spherical-shaped morphology at mesoscale while comprises interconnected primary nanoparticles at nanoscale. Such a unique morphology endows the h-LNCO with porous structure for easy penetration of electrolyte, relatively small size of primary particles with short Li+ ions diffusion length and abundant exposed surface in favor of Li+ intercalation/deintercalation. The synergism of these merits makes the h-LNCO exhibit superior electrochemical properties with high capacity, superior cyclability and rate capability, much better than the solid granular LNCO counterparts and commercial LiCoO2. This strategy of constructing porous hierarchical mesostructures could be extended to other electrode materials for electrochemical energy storage.

  3. A nanonet-enabled Li ion battery cathode material with high power rate, high capacity, and long cycle lifetime.

    PubMed

    Zhou, Sa; Yang, Xiaogang; Lin, Yongjing; Xie, Jin; Wang, Dunwei

    2012-01-24

    The performance of advanced energy conversion and storage devices, including solar cells and batteries, is intimately connected to the electrode designs at the nanoscale. Consider a rechargeable Li ion battery, a prevalent energy storage technology, as an example. Among other factors, the electrode material design at the nanoscale is key to realizing the goal of measuring fast ionic diffusion and high electronic conductivity, the inherent properties that determine power rates, and good stability upon repeated charge and discharge, which is critical to the sustainable high capacities. Here we show that such a goal can be achieved by forming heteronanostructures on a radically new platform we discovered, TiSi(2) nanonets. In addition to the benefits of high surface area, good electrical conductivity, and superb mechanical strength offered by the nanonet, the design also takes advantage of how TiSi(2) reacts with O(2) upon heating. The resulting TiSi(2)/V(2)O(5) nanostructures exhibit a specific capacity of 350 Ah/kg, a power rate up to 14.5 kW/kg, and 78.7% capacity retention after 9800 cycles of charge and discharge. These figures indicate that a cathode material significantly better than V(2)O(5) of other morphologies is produced.

  4. Solid-state synthesis and characterization of silver vanadium oxide for use as a cathode material for lithium batteries

    SciTech Connect

    Leising, R.A.; Takeuchi, E.S. )

    1994-04-01

    Silver vanadium oxide (SVO, AgV[sub 2]O[sub 5.5]) was synthesized for use as a cathode material in lithium/SVO batteries. The material was prepared via the solid-state thermal reaction of a silver-containing precursor and vanadium pentoxide at 500[degrees]C under an air or argon atmosphere. The silver-containing precursors examined in this study were silver nitrate, silver nitrite, silver vanadate, silver oxide, silver carbonate, and silver metal powder. SEM analysis of the SVO products indicated that the surface morphology was similar for each of the samples, with the dimensions of the rodlike particles depending on the form of silver used in the reaction. In addition, the degree of crystallinity of the samples depended strongly on the type of silver used in the reaction, as evidenced by X-ray powder diffraction analysis. All of the samples were analyzed by DSC, chemical analysis, X-ray powder diffraction, resistivity measurements, and electrical discharge tests of Li/SVO test cells. The experimental capacities and pulse power capabilities of the SVO samples prepared under an air atmosphere were all almost identical, while the samples synthesized under an inert atmosphere displayed a significant decrease in delivered capacity and pulse power capability. 40 refs., 6 figs., 8 tabs.

  5. Aspergillus flavus Conidia-derived Carbon/Sulfur Composite as a Cathode Material for High Performance Lithium-Sulfur Battery

    NASA Astrophysics Data System (ADS)

    Xu, Maowen; Jia, Min; Mao, Cuiping; Liu, Sangui; Bao, Shujuan; Jiang, Jian; Liu, Yang; Lu, Zhisong

    2016-01-01

    A novel approach was developed to prepare porous carbon materials with an extremely high surface area of 2459.6 m2g-1 by using Aspergillus flavus conidia as precursors. The porous carbon serves as a superior cathode material to anchor sulfur due to its uniform and tortuous morphology, enabling high capacity and good cycle lifetime in lithium sulfur-batteries. Under a current rate of 0.2 C, the carbon-sulfur composites with 56.7 wt% sulfur loading deliver an initial capacity of 1625 mAh g-1, which is almost equal to the theoretical capacity of sulfur. The good performance may be ascribed to excellent electronic networks constructed by the high-surface-area carbon species. Moreover, the semi-closed architecture of derived carbons can effectively retard the polysulfides dissolution during charge/discharge, resulting in a capacity of 940 mAh g-1 after 120 charge/discharge cycles.

  6. Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

    2014-04-01

    As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.

  7. Enhanced electrochemical performance in LiFePO4/graphene nanocomposite cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Dhindsa, Kulwinder; Mandal, B.; Lin, M. W.; Nazri, M.; Vaishnava, P.; Naik, V.; Nazri, G. A.; Naik, R.; Zhou, Z. X.

    2012-02-01

    We synthesized LiFePO4/graphene nano-composite employing a sol-gel method, where graphene oxide solution was added to the LiFePO4 precursors during the synthesis. Electrical measurement reveals that the addition of 10% graphene (by weight) to LiFePO4 increases its conductivity by 5 orders of magnitude. SEM images of the composite show that the material consists of LiFePO4 nanoparticles (with a mean particle size ˜ 50 nm) homogeneously mixed with graphene sheets; the latter provides a three-dimensional conducting network for Li+ ion and electron transport. A large specific capacity of 170 mAh/g was observed at a discharge rate of C/2. To further increase the conductivity and inhibit particle size growth of LiFePO4 (thus to increase the rate capacity), we coated the nanoparticles with a thin carbon layer by adding 0.25M lauric acid as precursor in addition to graphene oxide during the synthesis. The respective roles of graphene and lauric-acid-induced carbon coating in the specific capacity and charge-discharge rate of the LiFePO4 cathode material will be discussed.

  8. Triphenylamine-Based Metal-Organic Frameworks as Cathode Materials in Lithium-Ion Batteries with Coexistence of Redox Active Sites, High Working Voltage, and High Rate Stability.

    PubMed

    Peng, Zhe; Yi, Xiaohui; Liu, Zixuan; Shang, Jie; Wang, Deyu

    2016-06-15

    Through rational organization of two redox active building block, a triphenylamine-based metal-organic framework (MOF) material, Cu-TCA (H3TCA = tricarboxytriphenyl amine), was synthesized and applied as a cathode active material for the first time in lithium batteries. Cu-TCA exhibited redox activity both in the metal clusters (Cu(+)/Cu(2+)) and organic ligand radicals (N/N(+)) with separated voltage plateaus and a high working potential vs Li/Li(+) up to 4.3 V, comparing with the current commercial LiCoO2 cathode materials. The electrochemical behaviors of this MOF electrode material at different states of charge were carefully studied by cyclic voltammetry, X-ray photoelectron spectroscopy, and photoluminescence techniques. Long cycling stability of this MOF was achieved with an average Coulombic efficiency of 96.5% for 200 cycles at a 2 C rate. Discussing the electrochemical performances on the basis of capacity contributions from the metal clusters (Cu(+)/Cu(2+)) and organic ligands (N/N(+)) proposes an alternative mechanism of capacity loss for the MOF materials used in lithium batteries. This improved understanding will shed light on the designing principle of MOF-based cathode materials for their practical application in battery sciences. PMID:27225327

  9. Development program on a cold cathode electron gun

    NASA Technical Reports Server (NTRS)

    Spindt, C. A.; Holland, C. E.

    1985-01-01

    During this phase of the cathode development program, SRI improved the multiple electron beam exposure system used to print hole patterns for the cathode arrays, studied anisotropic etch processes, conducted cathode investigations using an emission microscope, reviewed possible alternate materials for cathode fabrication, studied cathode storage techniques, conducted high power operation experiments, and demonstrated high-current-density operation with small arrays of tips.

  10. Synthesis and Electrochemical Evaluation of Li, Mn-Rich Cathode Materials for Advanced Lithium Batteries.

    PubMed

    Yang, Sun-Woo; Kim, Min Young; Oh, Hyun; Lee, Moo Sung; Park, Sun-Il; Kim, Ho-Sung

    2016-02-01

    Li2MnO3-based composite, xLi2MnO3-(1--x)LiMO2 (M = Ni, Co, Mn, etc.), was synthesized via co-precipitation with sintering treatment. The composite material has hexagonal structure including a little of monoclinic with a nano-crystallite size. As a result, the material showed a specific redox behavior in the voltage range of 2.0-4.6 V and approximately 267 mAh/g of discharge capacity was obtained at the room temperature.

  11. Nonaqueous battery with organic compound cathode

    SciTech Connect

    Yamaji, A.; Yamaki, J.

    1981-02-17

    A battery embodying this invention comprises: an anode including an anode-active material formed of one metal selected from the Group IA metals or preferably lithium metal; a cathode including a cathode-active material formed of metal or metal-free organic compounds having a phthalocyanine function or organic compounds having a porphin function; and an electrolyte prepared from a material which is chemically stable to the cathode and anode materials and permits the migration of the ion of the anode metal to the cathode for electrochemical reaction with the cathode-active material.

  12. Arcjet Cathode Phenomena

    NASA Technical Reports Server (NTRS)

    Curran, Francis M.; Haag, Thomas W.; Raquet, John F.

    1989-01-01

    Cathode tips made from a number of different materials were tested in a modular arcjet thruster in order to examine cathode phenomena. Periodic disassembly and examination, along with the data collected during testing, indicated that all of the tungsten-based materials behaved similarly despite the fact that in one of these samples the percentage of thorium oxide was doubled and another was 25 percent rhenium. The mass loss rate from a 2 percent thoriated rhenium cathode was found to be an order of magnitude greater than that observed using 2 percent thoriated tungsten. Detailed analysis of one of these cathode tips showed that the molten crater contained pure tungsten to a depth of about 150 microns. Problems with thermal stress cracking were encountered in the testing of a hafnium carbide tip. Post test analysis showed that the active area of the tip had chemically reacted with the propellant. A 100 hour continuous test was run at about 1 kW. Post test analysis revealed no dendrite formation, such as observed in a 30 kW arcjet lifetest, near the cathode crater. The cathodes from both this test and a previously run 1000 hour cycled test displayed nearly identical arc craters. Data and calculations indicate that the mass losses observed in testing can be explained by evaporation.

  13. Arcjet cathode phenomena

    NASA Technical Reports Server (NTRS)

    Curran, Francis M.; Haag, Thomas W.; Raquet, John F.

    1989-01-01

    Cathode tips made from a number of different materials were tested in a modular arcjet thruster in order to examine cathode phenomena. Periodic disassembly and examination, along with the data collected during testing, indicated that all of the tungsten-based materials behaved similarly despite the fact that in one of these samples the percentage of thorium oxide was doubled and another was 25 percent rhenium. The mass loss rate from a 2 percent thoriated rhenium cathode was found to be an order of magnitude greater than that observed using 2 percent thoriated tungsten. Detailed analysis of one of these cathode tips showed that the molten crater contained pure tungsten to a depth of about 150 microns. Problems with thermal stress cracking were encountered in the testing of a hafnium carbide tip. Post test analysis showed that the active area of the tip had chemically reacted with the propellant. A 100 hour continuous test was run at about 1 kW. Post test analysis revealed no dendrite formation, such as observed in a 30 kW arcjet lifetest, near the cathode crater. The cathodes from both this test and a previously run 1000 hour cycled test displayed nearly identical arc craters. Data and calculations indicate that the mass losses observed in testing can be explained by evaporation.

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

    PubMed Central

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

    2015-01-01

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

  15. Carbon-coated LiFePO4-porous carbon composites as cathode materials for lithium ion batteries.

    PubMed

    Ni, Haifang; Liu, Jinkun; Fan, Li-Zhen

    2013-03-01

    This work introduces a facile strategy for the synthesis of carbon-coated LiFePO(4)-porous carbon (C-LiFePO(4)-PC) composites as a cathode material for lithium ion batteries. The LiFePO(4) particles obtained are about 200 nm in size and homogeneously dispersed in porous carbon matrix. These particles are further coated with the carbon layers pyrolyzed from sucrose. The C-LiFePO(4)-PC composites display a high initial discharge capacity of 152.3 mA h g(-1) at 0.1 C, good cycling stability, as well as excellent rate capability (112 mA h g(-1) at 5 C). The likely contributing factors to the excellent electrochemical performance of the C-LiFePO(4)-PC composites could be related to the combined effects of enhancement of conductivity by the porous carbon matrix and the carbon coating layers. It is believed that further carbon coating is a facile and effective way to improve the electrochemical performance of LiFePO(4)-PC.

  16. Systematic investigation on Cadmium-incorporation in Li₂FeSiO₄/C cathode material for lithium-ion batteries.

    PubMed

    Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

    2014-05-27

    Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li(+)-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material.

  17. A Na3V2(PO4)3 cathode material for use in hybrid lithium ion batteries.

    PubMed

    Song, Weixin; Ji, Xiaobo; Pan, Chengchi; Zhu, Yirong; Chen, Qiyuan; Banks, Craig E

    2013-09-14

    A NASICON-structure Na3V2(PO4)3 cathode material prepared by carbothermal reduction method is employed in a hybrid-ion battery with Li-involved electrolyte and anode. The ion-transportation mechanism is firstly investigated in this complicated system for an open three-dimensional framework Na3V2(PO4)3. Ion-exchange is greatly influenced by the standing time, for example, the 1 hour battery presents a specific capacity of 128 mA h g(-1) while the 24 hour battery exhibits a value of 148 mA h g(-1) with improved rate and cycling performances over existing literature reported Li-ion batteries. In the hybrid-ion system, an ion-exchange process likely takes place between the two Na(2) sites in the rhombohedral structure. NaLi2V2(PO4)3 could be produced by ion-transportation since the Na(+) in the Na(1) site is stationary and the three Na(2) sites could be used to accommodate the incoming alkali ions; Li(x)Na(y)V2(PO4)3 would come out when the vacant site in Na(2) was occupied depending on the applied voltage range. The reported methodology and power characteristics are greater than those previously reported.

  18. Electrochemical performance of spinel LiMn 2O 4 cathode materials made by flame-assisted spray technology

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaofeng; Zheng, Honghe; Battaglia, Vincent; Axelbaum, Richard L.

    Spinel lithium manganese oxide LiMn 2O 4 powders were synthesized by a flame-assisted spray technology (FAST) with a precursor solution consisting of stoichiometric amounts of LiNO 3 and Mn(NO 3) 2·4H 2O dissolved in methanol. The as-synthesized LiMn 2O 4 particles were non-agglomerated, and nanocrystalline. A small amount of Mn 3O 4was detected in the as-synthesized powder due to the decomposition of spinel LiMn 2O 4 at the high flame temperature. The impurity phase was removed with a post-annealing heat-treatment wherein the grain size of the annealed powder was 33 nm. The charge/discharge curves of both powders matched the characteristic plateaus of spinel LiMn 2O 4 at 3 V and 4 V vs. Li. However, the annealed powder showed a higher initial discharge capacity of 115 mAh g -1 at 4 V. The test cell with annealed powder showed good rate capability between a voltage of 3.0 and 4.3 V and a first cycle coulombic efficiency of 96%. The low coulombic efficiency from capacity fading may be due to oxygen defects in the annealed powder. The results suggest that FAST holds potential for rapid production of uniform cathode materials with low-cost nitrate precursors and minimal energy input.

  19. LiFePO4 - 3D carbon nanofiber composites as cathode materials for Li-ions batteries

    NASA Astrophysics Data System (ADS)

    Dimesso, L.; Spanheimer, C.; Jaegermann, W.; Zhang, Y.; Yarin, A. L.

    2012-03-01

    The characterization of carbon nanofiber 3D nonwovens, prepared by electrospinning process, coated with olivine structured lithium iron phosphate is reported. The LiFePO4 as cathode material for lithium ion batteries was prepared by a Pechini-assisted reversed polyol process. The coating has been successfully performed on carbon nanofiber 3D nonwovens by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 °C for 2-4 h. After drying-out, the composites were annealed at 600 °C for 5 h under nitrogen. The surface investigation of the prepared composites showed a uniform coating of the carbon nonwoven nanofibers as well as the formation of cauliflower-like crystalline structures which are uniformly distributed all over the surface area of the carbon nanofibers. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 156 mAhg- 1 at a discharging rate of C/25 and 152 mAhg- 1 at a discharging rate of C/10 at room temperature.

  20. Facile synthesis of porous Li2S@C composites as cathode materials for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Liang, Sheng; Liang, Chu; Xia, Yang; Xu, Haohui; Huang, Hui; Tao, Xinyong; Gan, Yongping; Zhang, Wenkui

    2016-02-01

    Lithium sulfide (Li2S) is regarded as a promising cathode material for lithium-sulfur (Li-S) batteries in terms of its high theoretical specific capacity of 1166 mAh g-1 and good compatibility with lithium metal-free anodes. However, Li2S suffers from poor cycling stability and rate capability resulted from the serious shuttle effect of lithium polysulfides and its low electronic and ionic conductivity. Here, we present a facile ball milling combined with carbon coating method to synthesize porous carbon-coated Li2S (Li2S@C) composites with a high Li2S content by using polystyrene (PS) as a carbon precursor. The Li2S@C composites show a high reversible specific capacity of 676 mAh g-1 (equal to 971 mAh g-1 sulfur) after 3 cycles at the current density of 0.1 A g-1, superior cycling stability with an average decay rate of 0.18% per cycle over 200 cycles, and improved rate capability of 416 mAh g-1 at the current density of 1.0 A g-1. The enhanced electrochemical properties of Li2S can be attributed to the porosity and core-shell structure of the Li2S@C composites, which increased the electronic and ionic conductivity of Li2S and alleviated the shuttle effect of intermediate lithium polysulfides in the discharge/charge process.

  1. Effect of titanium substitution in layered LiNiO 2 cathode material prepared by molten-salt synthesis

    NASA Astrophysics Data System (ADS)

    Ha, Hyung-Wook; Jeong, Kyung Hee; Kim, Keon

    LiNi 1- xTi xO 2 (0 ≤ x ≤ 0.1) compounds have been synthesized by a direct molten-salt method that uses a eutectic mixture of LiNO 3 and LiOH salts. According to X-ray diffraction analysis, these materials have a well-developed layered structure (R3-m) and are an isostructure of LiNiO 2. The LiNi 1- xTi xO 2 (0 ≤ x ≤ 0.1) compounds have average particle sizes of 1-5 μm depending on the amount of Ti salt. Charge-discharge tests show that a LiNi 1- xTi xO 2 (0 ≤ x ≤ 0.1) cathode prepared at 700 °C has an initial discharge capacity as high as 171 mA h g -1 and excellent capacity retention in the range 4.3-2.8 V at a current density of 0.2 mA cm -2.

  2. Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li-O2 Batteries.

    PubMed

    Wu, Feng; Xing, Yi; Li, Li; Qian, Ji; Qu, Wenjie; Wen, Jianguo; Miller, Dean; Ye, Yusheng; Chen, Renjie; Amine, Khalil; Lu, Jun

    2016-09-14

    To improve the electrochemical performance of the high energy Li-O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron-oxygen functional groups linking to the carbon surface or edge serve as additional reaction sites to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger interactions with Li5O6 clusters, so that B-rGO more effectively activates Li-O bonds to decompose Li2O2 during charge than rGO does. With B-rGO as a catalytic substrate, the Li-O2 battery achieves a high discharge capacity and excellent rate capability. Moreover, catalysts could be added into the B-rGO substrate to further lower the overpotential and enhance the cycling performance in future. PMID:27549204

  3. Systematic investigation on Cadmium-incorporation in Li₂FeSiO₄/C cathode material for lithium-ion batteries.

    PubMed

    Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

    2014-01-01

    Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li(+)-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material. PMID:24860942

  4. Li3V2(PO4)3 cathode materials for lithium-ion batteries: A review

    NASA Astrophysics Data System (ADS)

    Rui, Xianhong; Yan, Qingyu; Skyllas-Kazacos, Maria; Lim, Tuti Mariana

    2014-07-01

    The principal challenges facing the development of lithium ion batteries (LIBs) for hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles and for off-peak energy storage are cost, safety, cell energy density (voltage × capacity), rate of charge/discharge, and service life. There are exciting developments in new positive electrode (cathode) materials to replace the LiCoO2 for use in the LIBs over the past decade. Monoclinic Li3V2(PO4)3 (LVP) with promising electrochemical properties including excellent cycling stability, high theoretical capacity (197 mAh g-1), low synthetic cost, improved safety characteristic, and low environmental impact emerges as highly suitable candidate. In this review, we focus on research work related to the LVP and discuss its host structure, mechanism of lithium insertion/extraction, transport properties (i.e., electronic conductivity, and lithium diffusion), synthesis and electrochemical properties. We highlight some recent development of LVP, which shows superior cycling stability and high rate capability and give some vision for the future research of LVP based electrodes.

  5. Synthesis, morphological analysis and electrochemical performance of iron hydroxyl phosphate as a cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Shi Ming; Zhang, Jun Xi; Xu, Suo Jiong; Yuan, Xu Jie; Tan, Tian

    2013-12-01

    Iron hydroxyl phosphate, with the formula Fe1.5(PO4)(OH), used as a cathode material in lithium ion batteries, is synthesised by a sample hydrothermal method. Scanning electron microscopy (SEM), X-ray diffraction and galvanostatical charge/discharge tests are employed to characterise the morphology, structure and electrochemical performance of the iron hydroxyl phosphate, respectively. FE-SEM shows that the morphologies are closely related to the hydrothermal temperatures at which they are synthesised. The morphologies, such as spherical, cubic, multi-armed and cross-like structures, could be easily regulated by adjusting the hydrothermal temperature. It is found that different morphologies of iron hydroxyl phosphate gave rise to different electrochemical performances. Compared to the others, iron hydroxyl phosphate spherical composites exhibit not only a high reversible capacity but also good cycling stability, with a reversible initial discharge specific capacity of around 176 mAh g-1 and a remaining 95% of the initial discharge specific capacity after 60 cycles at 0.1C. The improved electrochemical performance is attributed to the spherical morphology and smaller particle size, which increase the reaction interfaces and shorten the diffusion distance of the lithium ions.

  6. Layer cathode methods of manufacturing and materials for Li-ion rechargeable batteries

    DOEpatents

    Kang, Sun-Ho; Amine, Khalil

    2008-01-01

    A positive electrode active material for lithium-ion rechargeable batteries of general formula Li.sub.1+xNi.sub..alpha.Mn.sub..beta.A.sub..gamma.O.sub.2 and further wherein A is Mg, Zn, Al, Co, Ga, B, Zr, or Ti and 0material is manufactured by employing either a solid state reaction method or an aqueous solution method or a sol-gel method which is followed by a rapid quenching from high temperatures into liquid nitrogen or liquid helium.

  7. Mixed Electronic and Ionic Conductor-Coated Cathode Material for High-Voltage Lithium Ion Battery.

    PubMed

    Shim, Jae-Hyun; Han, Jung-Min; Lee, Joon-Hyung; Lee, Sanghun

    2016-05-18

    A lithium ionic conductor, Li1.3Al0.3Ti1.7(PO4)3 (LATP), is introduced as a coating material on the surface of Mg-doped LiCoO2 to improve electrochemical performances for high-voltage (4.5 V) lithium ion batteries. Structure, morphology, elemental distribution, and electrical properties of the materials are thoroughly characterized by SEM, TEM, EELS, EDS, and C-AFM. The coating layer is electrically conductive with the aid of Mg ions which are used as a dopant for the active materials; therefore, this mixed electronic ionic conductor strongly enhances the electrochemical performances of initial capacity, cycling property, and rate capability. The LATP coating layer also demonstrates very promising applicability for 4.4 V prismatic full cells with graphite anode, which correspond to the 4.5 V half-cells with lithium anode. The 2900 mA h full cells show 85% of capacity retention after 500 cycles and more than 60% after 700 cycles.

  8. Mixed Electronic and Ionic Conductor-Coated Cathode Material for High-Voltage Lithium Ion Battery.

    PubMed

    Shim, Jae-Hyun; Han, Jung-Min; Lee, Joon-Hyung; Lee, Sanghun

    2016-05-18

    A lithium ionic conductor, Li1.3Al0.3Ti1.7(PO4)3 (LATP), is introduced as a coating material on the surface of Mg-doped LiCoO2 to improve electrochemical performances for high-voltage (4.5 V) lithium ion batteries. Structure, morphology, elemental distribution, and electrical properties of the materials are thoroughly characterized by SEM, TEM, EELS, EDS, and C-AFM. The coating layer is electrically conductive with the aid of Mg ions which are used as a dopant for the active materials; therefore, this mixed electronic ionic conductor strongly enhances the electrochemical performances of initial capacity, cycling property, and rate capability. The LATP coating layer also demonstrates very promising applicability for 4.4 V prismatic full cells with graphite anode, which correspond to the 4.5 V half-cells with lithium anode. The 2900 mA h full cells show 85% of capacity retention after 500 cycles and more than 60% after 700 cycles. PMID:27127906

  9. Ab initio study of vacancy formation in cubic LaMnO3 and SmCoO3 as cathode materials in solid oxide fuel cells.

    PubMed

    Olsson, Emilia; Aparicio-Anglès, Xavier; de Leeuw, Nora H

    2016-07-01

    Doped LaMnO3 and SmCoO3 are important solid oxide fuel cell cathode materials. The main difference between these two perovskites is that SmCoO3 has proven to be a more efficient cathode material than LaMnO3 at lower temperatures. In order to explain the difference in efficiency, we need to gain insight into the materials' properties at the atomic level. However, while LaMnO3 has been widely studied, ab initio studies on SmCoO3 are rare. Hence, in this paper, we perform a comparative DFT + U study of the structural, electronic, and magnetic properties of these two perovskites. To that end, we first determined a suitable Hubbard parameter for the Co d-electrons to obtain a proper description of SmCoO3 that fully agrees with the available experimental data. We next evaluated the impact of oxygen and cation vacancies on the geometry, electronic, and magnetic properties. Oxygen vacancies strongly alter the electronic and magnetic structures of SmCoO3, but barely affect LaMnO3. However, due to their high formation energy, their concentrations in the material are very low and need to be induced by doping. Studying the cation vacancy concentration showed that the formation of cation vacancies is less energetically favorable than oxygen vacancies and would thus not markedly influence the performance of the cathode. PMID:27394117

  10. Ab initio study of vacancy formation in cubic LaMnO3 and SmCoO3 as cathode materials in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Olsson, Emilia; Aparicio-Anglès, Xavier; de Leeuw, Nora H.

    2016-07-01

    Doped LaMnO3 and SmCoO3 are important solid oxide fuel cell cathode materials. The main difference between these two perovskites is that SmCoO3 has proven to be a more efficient cathode material than LaMnO3 at lower temperatures. In order to explain the difference in efficiency, we need to gain insight into the materials' properties at the atomic level. However, while LaMnO3 has been widely studied, ab initio studies on SmCoO3 are rare. Hence, in this paper, we perform a comparative DFT + U study of the structural, electronic, and magnetic properties of these two perovskites. To that end, we first determined a suitable Hubbard parameter for the Co d-electrons to obtain a proper description of SmCoO3 that fully agrees with the available experimental data. We next evaluated the impact of oxygen and cation vacancies on the geometry, electronic, and magnetic properties. Oxygen vacancies strongly alter the electronic and magnetic structures of SmCoO3, but barely affect LaMnO3. However, due to their high formation energy, their concentrations in the material are very low and need to be induced by doping. Studying the cation vacancy concentration showed that the formation of cation vacancies is less energetically favorable than oxygen vacancies and would thus not markedly influence the performance of the cathode.

  11. A nanocomposite of Li2MnO3 coated by FePO4 as cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Faxing; Xiao, Shiying; Li, Minxia; Wang, Xiaowei; Zhu, Yusong; Wu, Yuping; Shirakawa, Akihiko; Peng, Jun

    2015-08-01

    A core-shell nanocomposite of Li2MnO3 is synthesized by coating FePO4 nanoparticles on the surface of our prepared Li2MnO3 nanoplate. This core-shell structured nanocomposite can eliminate the large irreversible capacity for the Li-rich materials. The FePO4 on the surface of Li2MnO3 can also serve as a host for Li ions that deintercalate from Li2MnO3 during the initial charging process and the initial Coulomb efficiency can be 100%. The composite as the cathode material for lithium ion batteries exhibits an attractive reversible capacity of 180 mAh g-1. Its cycling performance is also stable without any evident capacity fading, even when cycling in the high voltage range of 2.0-4.8 V vs. Li+/Li. This nanocomposite is free of Co- and Ni, different from other Li-rich Li2MnO3 based cathode materials, and shows great attraction for applications of low cost cathode materials for lithium ion batteries.

  12. A Bifunctional Interlayer Material for Modifying Both the Anode and Cathode in Highly Efficient Polymer Solar Cells.

    PubMed

    Xu, Bowei; Zheng, Zhong; Zhao, Kang; Hou, Jianhui

    2016-01-20

    A novel polymer-solar-cell architecture using the conjugated polymer PFS as both the anode and cathode interlayers is constructed, and a high power conversion efficiency of 9.48% is achieved using the corresponding photovoltaic device.

  13. Heteroatomic SenS8-n Molecules Confined in Nitrogen-Doped Mesoporous Carbons as Reversible Cathode Materials for High-Performance Lithium Batteries.

    PubMed

    Sun, Fugen; Cheng, Hongye; Chen, Jianzhuang; Zheng, Nan; Li, Yongsheng; Shi, Jianlin

    2016-09-27

    A reversible cathode material in an ether-based electrolyte for high-energy lithium batteries was successfully fabricated by homogeneously confining heteroatomic SenS8-n molecules into nitrogen-doped mesoporous carbons (NMCs) via a facile melt-impregnation route. The resultant SenS8-n/NMC composites exhibit highly reversible electrochemical behavior, where selenium sulfides are recovered through the reversible conversion of polysulfoselenide intermediates during discharge-charge cycles. The recovery of selenium sulfide molecules endows the SenS8-n/NMC cathodes with the rational integration of S and Se cathodes. Density functional theory calculations further reveal that heteroatomic selenium sulfide molecules with higher polarizability could bind more strongly with NMCs than homoatomic sulfur molecules, which provides more efficient suppression of the shuttling phenomenon. Therefore, with further assistance of mesopore confinement of the nitrogen-doped carbons, the Se2S6/NMC composite with an optimal Se/S mole ratio of 2/6 presents excellent cycle stability with a high initial Coulombic efficiency of 96.5% and a high reversible capacity of 883 mAh g(-1) after 100 cycles and 780 mAh g(-1) after 200 cycles at 250 mA g(-1). These encouraging results suggest that the heteroatomization of chalcogen (such as S, Se, or Te) molecules in mesostructured carbon hosts is a promising strategy in enhancing the electrochemical performances of chalcogen/carbon-based cathodes for Li batteries. PMID:27522865

  14. Heteroatomic SenS8-n Molecules Confined in Nitrogen-Doped Mesoporous Carbons as Reversible Cathode Materials for High-Performance Lithium Batteries.

    PubMed

    Sun, Fugen; Cheng, Hongye; Chen, Jianzhuang; Zheng, Nan; Li, Yongsheng; Shi, Jianlin

    2016-09-27

    A reversible cathode material in an ether-based electrolyte for high-energy lithium batteries was successfully fabricated by homogeneously confining heteroatomic SenS8-n molecules into nitrogen-doped mesoporous carbons (NMCs) via a facile melt-impregnation route. The resultant SenS8-n/NMC composites exhibit highly reversible electrochemical behavior, where selenium sulfides are recovered through the reversible conversion of polysulfoselenide intermediates during discharge-charge cycles. The recovery of selenium sulfide molecules endows the SenS8-n/NMC cathodes with the rational integration of S and Se cathodes. Density functional theory calculations further reveal that heteroatomic selenium sulfide molecules with higher polarizability could bind more strongly with NMCs than homoatomic sulfur molecules, which provides more efficient suppression of the shuttling phenomenon. Therefore, with further assistance of mesopore confinement of the nitrogen-doped carbons, the Se2S6/NMC composite with an optimal Se/S mole ratio of 2/6 presents excellent cycle stability with a high initial Coulombic efficiency of 96.5% and a high reversible capacity of 883 mAh g(-1) after 100 cycles and 780 mAh g(-1) after 200 cycles at 250 mA g(-1). These encouraging results suggest that the heteroatomization of chalcogen (such as S, Se, or Te) molecules in mesostructured carbon hosts is a promising strategy in enhancing the electrochemical performances of chalcogen/carbon-based cathodes for Li batteries.

  15. Understanding the effects of a multi-functionalized additive on the cathode-electrolyte interfacial stability of Ni-rich materials

    NASA Astrophysics Data System (ADS)

    Yim, Taeeun; Kang, Kyoung Seok; Mun, Junyoung; Lim, Sang Hoo; Woo, Sang-Gil; Kim, Ki Jae; Park, Min-Sik; Cho, Woosuk; Song, Jun Ho; Han, Young-Kyu; Yu, Ji-Sang; Kim, Young-Jun

    2016-01-01

    Nickel-rich lithium nickel cobalt manganese oxides have received considerable attention as a promising cathode material, however, they have suffered from poor interfacial stability, especially at high temperature. Here, we suggest a bi-functionalized divinyl sulfone that enhances the applicability of a nickel-rich cathode via stabilization of the electrolyte-electrode interface. The divinyl sulfone forms a protective layer on the cathode surface by electrochemical oxidation reactions and this greatly decreases the internal pressure of the cell via stabilization of the Ni-rich cathode-electrolyte interface. The cell controlled with divinyl sulfone shows remarkable cycling performance with 91.9% capacity retention at elevated temperature even after 100 cycles. Additional electrode analyses and first-principles calculations provide critical spectroscopic evidences to demonstrate the combined effects of the sulfone and vinyl functional groups. Once the divinyl sulfone is electrochemically oxidized, the vinyl functional groups readily participate in further stabilizing sulfone-based solid electrolyte interphase intermediates and afford a durable protective layer on the nickel-rich electrode surface.

  16. Structural predictions based on the compositions of cathodic materials by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Li, Yang; Lian, Fang; Chen, Ning; Hao, Zhen-jia; Chou, Kuo-chih

    2015-05-01

    A first-principles method is applied to comparatively study the stability of lithium metal oxides with layered or spinel structures to predict the most energetically favorable structure for different compositions. The binding and reaction energies of the real or virtual layered LiMO2 and spinel LiM2O4 (M = Sc-Cu, Y-Ag, Mg-Sr, and Al-In) are calculated. The effect of element M on the structural stability, especially in the case of multiple-cation compounds, is discussed herein. The calculation results indicate that the phase stability depends on both the binding and reaction energies. The oxidation state of element M also plays a role in determining the dominant structure, i.e., layered or spinel phase. Moreover, calculation-based theoretical predictions of the phase stability of the doped materials agree with the previously reported experimental data.

  17. High-temperature electrical testing of a solid oxide fuel cell cathode contact material

    SciTech Connect

    Weil, K. Scott

    2004-06-01

    The development of high temperature solid state devices for energy generation and environmental control applications has advanced remarkably over the past decade. However, there remain a number technical barriers that still impede widespread commercial application. One of these, for example, is the development of a robust method of conductively joining the mixed-conducting oxide electrodes that lie at the heart of the device to the heat resistant metal interconnect used to transmit power to or from the electrodes and electrochemically active membrane. In the present study, we have investigated the high-temperature electrical and microstructural characteristics of a series of conductive glass composite paste junctions between two contact materials representative of those employed in solid-state electrochemical devices, lanthanum calcium manganate and 430 stainless steel.

  18. High-temperature electrical testing of a solid oxide fuel cell cathode contact material

    NASA Astrophysics Data System (ADS)

    Weil, K. Scott

    2004-06-01

    The development of high-temperature solid-state devices for energy generation and environmental control applications has advanced remarkably over the past decade. However, there remain a number of technical barriers that still impede widespread commercial application. One of these, for example, is the development of a robust method of conductively joining the mixed-conducting oxide electrodes that lie at the heart of the device to the heat resistant metal interconnect used to transmit power to or from the electrodes and electrochemically active membrane. This study investigated the high-temperature electrical and microstructural characteristics of a series of conductive glass composite paste junctions between two contact materials representative of those used in solid-state electrochemical devices, lanthanum calcium manganate, and 430 stainless steel.

  19. Designing and Thermal Analysis of Safe Lithium Ion Cathode Materials for High Energy Applications

    NASA Astrophysics Data System (ADS)

    Hu, Enyuan

    Safety is one of the most critical issues facing lithium-ion battery application in vehicles. Addressing this issue requires the integration of several aspects, especially the material chemistry and the battery thermal management. First, thermal stability investigation was carried out on an attractive high energy density material LiNi0.5Mn1.5O4. New findings on the thermal-stability and thermal-decomposition-pathways related to the oxygen-release are discovered for the high-voltage spinel Li xNi0.5Mn1.5O4 (LNMO) with ordered (o-) and disordered (d-) structures at fully delithiated (charged) state using a combination of in situ time-resolved x-ray diffraction (TR-XRD) coupled with mass spectroscopy (MS) and x-ray absorption spectroscopy (XAS). Both fully charged o--LixNi0.5Mn1.5O 4 and d-LixNi0.5Mn1.5O 4 start oxygen-releasing structural changes at temperatures below 300 °C, which is in sharp contrast to the good thermal stability of the 4V-spinel LixMn2O4 with no oxygen being released up to 375 °C. This is mainly caused by the presence of Ni4+ in LNMO, which undergoes dramatic reduction during the thermal decomposition. In addition, charged o-LNMO shows better thermal stability than the d-LNMO counterpart, due to the Ni/Mn ordering and smaller amount of the rock-salt impurity phase in o-LNMO. Newly identified two thermal-decomposition-pathways from the initial LixNi0.5Mn1.5O 4 spinel to the final NiMn2O4-type spinel structure with and without the intermediate phases (NiMnO3 and alpha-Mn 2O3) are found to play key roles in thermal stability and oxygen release of LNMO during thermal decomposition. In addressing the safety issue associated with LNMO, Fe is selected to partially substitute Ni and Mn simultaneously utilizing the electrochemical activity and structure-stabilizing high spin Fe3+. The synthesized LiNi1/3Mn4/3Fe1/3O4 showed superior thermal stability and satisfactory electrochemical performance. At charged state, it is able to withstand the temperature as

  20. An efficient electrocatalyst as cathode material for solid oxide fuel cells: BaFe0·95Sn0·05O3-δ

    NASA Astrophysics Data System (ADS)

    Dong, Feifei; Ni, Meng; He, Wei; Chen, Yubo; Yang, Guangming; Chen, Dengjie; Shao, Zongping

    2016-09-01

    The B-site substitution with the minor amount of tin in BaFeO3-δ parent oxide is expected to stabilize a single perovskite lattice structure. In this study, a composition of BaFe0·95Sn0·05O3-δ (BFS) as a new cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is synthesized and characterized. Special attention is paid to the exploration of some basic properties including phase structure, oxygen non-stoichiometry, electrical conductivity, oxygen bulk diffusion coefficient, and surface exchange coefficient, which are of significant importance to the electrochemical activity of cathode materials. BFS holds a single cubic perovskite structure over temperature range of cell operation, determined by in-situ X-ray diffraction and scanning transmission electron microscope. A high oxygen vacancy concentration at cell operating temperatures is observed by combining thermo-gravimetric data and iodometric titration result. Furthermore, electrical conductivity relaxation measurement illustrates the fast oxygen bulk diffusion and surface exchange kinetics. Accordingly, testing cells based on BFS cathode material demonstrate the low polarization resistance of 0.033 Ω cm2 and high peak power density of 1033 mW cm-2 at 700 °C, as well as a relatively stable long-term operation for ∼300 h. The results obtained suggest that BFS perovskite oxide holds a great promise as an oxygen reduction electrocatalyst for IT-SOFCs.

  1. Discharge/charge reaction mechanisms of FeS2 cathode material for aluminum rechargeable batteries at 55°C

    NASA Astrophysics Data System (ADS)

    Mori, Takuya; Orikasa, Yuki; Nakanishi, Koji; Kezheng, Chen; Hattori, Masashi; Ohta, Toshiaki; Uchimoto, Yoshiharu

    2016-05-01

    The aluminum rechargeable battery is a desirable device for large-scale energy storage owing to the high capacity derived from the properties of the aluminum metal anode. The development of cathode materials is needed to compose battery systems. However, the design principles of the cathode materials have not been determined. We focus on the high capacity FeS2 cathode materials and investigate the discharge/charge reaction mechanisms in chloroaluminate ionic liquids as the electrolyte at 55°C. X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements are performed for the discharged and charged samples. S 3p-orbitals are shown to play an important role in the redox reactions from the results of the S and Fe K-edge XANES spectra. As a result of the redox reaction, FeS2 is transformed into low crystalline FeS and amorphous Al2S3, as shown by the XRD and S, Al, and Fe K-edge XANES spectra. This reaction mechanism is different from the reaction observed with lithium ion.

  2. Preparation, structure study and electrochemistry of layered H2V3O8 materials: High capacity lithium-ion battery cathode

    NASA Astrophysics Data System (ADS)

    Sarkar, Sudeep; Bhowmik, Arghya; Pan, Jaysree; Bharadwaj, Mridula Dixit; Mitra, Sagar

    2016-10-01

    The present study explores H2V3O8 as high capacity cathode material for lithium-ion batteries (LIB's). Despite having high discharge capacity, H2V3O8 material suffers from poor electrochemical stability for prolonged cycle life. Ultra-long H2V3O8 nanobelts with ordered crystallographic patterns are synthesized via a hydrothermal process to mitigate this problem. The growth of the crystal is facile along [001] direction, and the most common surface is (001) as suggested by Wulff construction study. Electrochemical performance of H2V3O8 cathode is tested against Li/Li+ at various current rates. At 50 mA g-1current rate, it delivers a discharge capacity of 308 mAh g-1, whereas, at 3000 mA g-1, an initial discharge capacity of 144 mAh g-1 is observed and stabilized at 100 mAh g-1 till 500 cycles. Further, the density functional theory (DFT) based simulations study of both the pristine and lithiated phase of H2V3O8 cathode materials is undertaken. DFT study reveals the presence of hydrogen as hydroxyl unit in the framework of the host. In correlation, the magnetic property of vanadium atoms is examined in detail with through partial density of states (PDOS) calculation during three stage lithiation processes and evaluating various potential steps involved in lithium insertion.

  3. Nitrogen-doped graphene-decorated LiVPO4F nanocomposite as high-voltage cathode material for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Cui, Kai; Hu, Shuchun; Li, Yongkui

    2016-09-01

    In this study, nitrogen-doped graphene decorated LiVPO4F cathode material is firstly synthesized via a facile method. Well-dispersed LiVPO4F nanoparticles are embedded in nitrogen-doped graphene nanosheets, forming an effective conducting network. The added nitrogen-doped graphene nanosheets greatly enhance the electronic conductivity and Li-ion diffusion of LiVPO4F sample. When tested as cathode material for rechargeable lithium-ion batteries, the hybrid electrode exhibits superior high-rate performance and long-term cycling stability between 3.0 and 4.5 V. It delivers a large discharge capacity of 152.7 mAhg-1 at 0.1 C and shows a capacity retention of 97.8% after 60 cycles. Moreover, a reversible capacity of 90.1 mAhg-1 is maintained even after 500 cycles at a high rate of 20 C. The charge-transfer resistance of LiVPO4F electrode is also reduced in the nitrogen-doped graphene, revealing that its electrode-electrolyte complex reactions take place easily and thus improve the electrochemical performance. The above results provide a facile and effective strategy for the synthesis of LiVPO4F cathode material for high-performance lithium-ion batteries.

  4. Enhanced rate performance of multiwalled carbon nanotube encrusted olivine type composite cathode material using polyol technique

    NASA Astrophysics Data System (ADS)

    Muruganantham, R.; Sivakumar, M.; Subadevi, R.

    2015-12-01

    Olivine type multi-walled carbon nanotube encrusted LiFePO4/C composites have been prepared using economic and energy efficient simple polyol technique without any subsequent heat treatment. The prepared material has an olivine type orthorhombic phase. Also, the iron oxidation state is 2+, which is identified by X-ray diffraction and X-ray photoelectron spectroscopy. It is possible to attain the discharge capacity almost close to theoretical capacity of LiFePO4 as in high temperature methods with ∼100% coulombic efficiency. The specific surface area has been increased upon encrusting multi walled carbon nano tube on LiFePO4/C, which results in enhanced reversible capacity upto 166 mAh g-1 at C/10. Also, it exhibits 89 mAh g-1 even at 30 C rate. This is due to the formation of conductive networks by carbon nanotube, and excellent attachment of LiFePO4/C composite particles on multi-walled carbon nanotube, which induced the kinetics during intercalation/deintercalation process. Multi-walled carbon nanotube acts as the electro-conductive filler on the LiFePO4 surface. The direct addition of MWCNT would result better performances than blending the MWCNT with LiFePO4/C.

  5. Hierarchical sulfur-based cathode materials with long cycle life for rechargeable lithium batteries.

    PubMed

    Wang, Jiulin; Yin, Lichao; Jia, Hao; Yu, Haitao; He, Yushi; Yang, Jun; Monroe, Charles W

    2014-02-01

    Composite materials of porous pyrolyzed polyacrylonitrile-sulfur@graphene nanosheet (pPAN-S@GNS) are fabricated through a bottom-up strategy. Microspherical particles are formed by spray drying of a mixed aqueous colloid of PAN nanoparticles and graphene nanosheets, followed by a simple heat treatment with elemental sulfur. The pPAN-S primary nanoparticles are wrapped homogeneously and loosely within a three-dimensional network of graphene nanosheets (GNS). The hierarchical pPAN-S@GNS composite shows a high reversible capacity of 1449.3 mAh g(-1) sulfur or 681.2 mAh g(-1) composite in the second cycle; after 300 cycles at a 0.2 C charge/discharge rate the capacity retention is 88.8 % of its initial reversible value. Additionally, the coulombic efficiency (CE) during cycling is near 100 %, apart from in the first cycle, in which CE is 81.1 %. A remarkable capacity of near 700 mAh g(-1) sulfur is obtained, even at a high discharge rate of 10 C. The superior performance of pPAN-S@GNS is ascribed to the spherical secondary GNS structure that creates an electronically conductive 3D framework and also reinforces structural stability. PMID:24155121

  6. Infiltrating sulfur into a highly porous carbon sphere as cathode material for lithium–sulfur batteries

    SciTech Connect

    Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Hyo-Jun; Kim, Ki-Won; Cho, Kwon-Koo; Ahn, Jou-Hyeon

    2014-10-15

    Highlights: • A highly porous carbon (HPC) with regular spherical morphology was synthesized. • Sulfur/HPC composites were prepared by melt–diffusion method. • Sulfur/HPC composites showed improved cyclablity and long-term cycle life. - Abstract: Sulfur composite material with a highly porous carbon sphere as the conducting container was prepared. The highly porous carbon sphere was easily synthesized with resorcinol–formaldehyde precursor as the carbon source. The morphology of the carbon was observed with field emission scanning electron microscope and transmission electron microscope, which showed a well-defined spherical shape. Brunauer–Emmett–Teller analysis indicated that it possesses a high specific surface area of 1563 m{sup 2} g{sup −1} and a total pore volume of 2.66 cm{sup 3} g{sup −1} with a bimodal pore size distribution, which allow high sulfur loading and easy transportation of lithium ions. Sulfur carbon composites with varied sulfur contents were prepared by melt–diffusion method and lithium sulfur cells with the sulfur composites showed improved cyclablity and long-term cycle life.

  7. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials.

    PubMed

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-01-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe(3+) ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe(3+) on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries. PMID:27293181

  8. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials

    PubMed Central

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-01-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe3+ ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe3+ on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries. PMID:27293181

  9. New materials for Li-ion batteries: synthesis and spectroscopic characterization of Li2(FeMnCo)SiO4 cathode materials

    NASA Astrophysics Data System (ADS)

    Ferrari, Stefania; Mozzati, Maria Cristina; Lantieri, Marco; Spina, Gabriele; Capsoni, Doretta; Bini, Marcella

    2016-06-01

    Improving cathode materials is mandatory for next-generation Li-ion batteries. Exploring polyanion compounds with high theoretical capacity such as the lithium metal orthosilicates, Li2MSiO4 is of great importance. In particular, mixed silicates represent an advancement with practical applications. Here we present results on a rapid solid state synthesis of mixed Li2(FeMnCo)SiO4 samples in a wide compositional range. The solid solution in the P21/n space group was found to be stable for high iron concentration or for a cobalt content up to about 0.3 atom per formula unit. Other compositions led to a mixture of polymorphs, namely Pmn21 and Pbn21. All the samples contained a variable amount of Fe3+ ions that was quantified by Mössbauer spectroscopy and confirmed by the TN values of the paramagnetic to antiferromagnetic transition. Preliminary characterization by cyclic voltammetry revealed the effect of Fe3+ on the electrochemical response. Further work is required to determine the impact of these electrode materials on lithium batteries.

  10. Cathodic arcs

    SciTech Connect

    Anders, Andre

    2003-10-29

    Cathodic arc plasma deposition has become the technology of choice for hard, wear and corrosion resistant coatings for a variety of applications. The history, basic physics of cathodic arc operation, the infamous macroparticle problem and common filter solutions, and emerging high-tech applications are briefly reviewed. Cathodic arc plasmas standout due to their high degree of ionization, with important consequences for film nucleation, growth, and efficient utilization of substrate bias. Industrial processes often use cathodic arc plasma in reactive mode. In contrast, the science of arcs has focused on the case of vacuum arcs. Future research directions include closing the knowledge gap for reactive mode, large area coating, linear sources and filters, metal plasma immersion process, with application in high-tech and biomedical fields.

  11. Cathode for aluminum producing electrolytic cell

    DOEpatents

    Brown, Craig W.

    2004-04-13

    A method of producing aluminum in an electrolytic cell comprising the steps of providing an anode in a cell, preferably a non-reactive anode, and also providing a cathode in the cell, the cathode comprised of a base material having low electrical conductivity reactive with molten aluminum to provide a highly electrically conductive layer on the base material. Electric current is passed from the anode to the cathode and alumina is reduced and aluminum is deposited at the cathode. The cathode base material is selected from boron carbide, and zirconium oxide.

  12. REACTIVE FORCE FIELDS FOR Y-DOPED BaZrO3 ELECTROLYTE AND NI-ANODE. POTENTIAL CATHODE MATERIALS FOR APPLICATION IN PROTON CERAMIC FUEL CELLS

    SciTech Connect

    Boris Merinov; Adri van Duin; Sossina Haile; William A. Goddard III

    2004-10-30

    Based on quantum mechanical data obtained for the Y-doped BaZrO{sub 3} electrolyte and Ni-anode Reactive Force Field parameters have been developed for further molecular dynamics simulations of the proton diffusion and electrode/electrolyte interfaces. Electronic and atomic structures of different terminations of the (001) BaZrO{sub 3} surface have been studied using first-principles calculations. Several potential cathode materials for the Y-doped BaZrO{sub 3} system were synthesized via glycine nitrate combustion method. Of the five potential cathode materials examined BaZr{sub 0.40}Pr{sub 0.40}Gd{sub 0.20}O{sub 3} and BaZr{sub 0.60}Y{sub 0.20}Co{sub 0.20}O{sub 3} appear to be the most promising for further applications in proton ceramic fuel cells. Fuel cell test of a Y-doped BaZrO{sub 3} thin film using platinum ink for both electrodes have been performed. The obtained results shows that a robust method for fabricating crack-free thin membranes, as well as methods for sealing anode and cathode chambers, have successfully been developed.

  13. Lithiated Vanadium Oxide (LVO), gamma-lithium vanadium bronze (Gamma-LIV2O5) and vanadium dioxide (VO2) as thermal battery cathode materials

    NASA Astrophysics Data System (ADS)

    Richie, A. G.; Warner, K.

    1991-05-01

    Thermal batteries are high temperature reserve batteries, predominantly used in missiles. Modern designs use a lithium (or lithium alloy) anode, an immobilized molten salt electrolyte, and an iron-disulphide cathode. These batteries have many advantages: high reliability, long storage life without maintenance, wide temperature range of operation, and, sometimes, high power. However, the energy density is rather low and this could be improved if the individual cell voltage could be raised above the present 2.2 V/cell open circuit-voltage for the lithium iron-disulphide couple. A new cathode material, lithiated vanadium oxide (LVO), was invented at RAE and has the advantage of a much higher open-circuit voltage of 2.6 V/cell versus lithium. The properties of LVO have been investigated and it has been shown that LVO consists of vanadium dioxide as the major component. Some lithium bromide is also present.

  14. Core-shell nano-FeS2@N-doped graphene as an advanced cathode material for rechargeable Li-ion batteries.

    PubMed

    Tan, Rui; Yang, Jinlong; Hu, Jiangtao; Wang, Kai; Zhao, Yan; Pan, Feng

    2016-01-18

    We report the formation of core-shell nano-FeS2@N-doped graphene as a novel cathode material and its mechanism for use in rechargeable Li-ion batteries. A benefit of the amount of FeS2 nano-crystals as the core for Li-ion storage with high capacity and using coated N-doped graphene as the shell is that FeS2@N-graphene exhibits a remarkable specific energy (950 W h kg(-1) at 0.15 kW g(-1)) and higher specific power (543 W h kg(-1) at 2.79 kW g(-1)) than commercial rechargeable LIB cathodes, as well as stable cycling performance (∼600 W h kg(-1) at 0.75 kW g(-1) after 400 cycles).

  15. Nanotube cathodes.

    SciTech Connect

    Overmyer, Donald L.; Lockner, Thomas Ramsbeck; Siegal, Michael P.; Miller, Paul Albert

    2006-11-01

    Carbon nanotubes have shown promise for applications in many diverse areas of technology. In this report we describe our efforts to develop high-current cathodes from a variety of nanotubes deposited under a variety of conditions. Our goal was to develop a one-inch-diameter cathode capable of emitting 10 amperes of electron current for one second with an applied potential of 50 kV. This combination of current and pulse duration significantly exceeds previously reported nanotube-cathode performance. This project was planned for two years duration. In the first year, we tested the electron-emission characteristics of nanotube arrays fabricated under a variety of conditions. In the second year, we planned to select the best processing conditions, to fabricate larger cathode samples, and to test them on a high-power relativistic electron beam generator. In the first year, much effort was made to control nanotube arrays in terms of nanotube diameter and average spacing apart. When the project began, we believed that nanotubes approximately 10 nm in diameter would yield sufficient electron emission properties, based on the work of others in the field. Therefore, much of our focus was placed on measured field emission from such nanotubes grown on a variety of metallized surfaces and with varying average spacing between individual nanotubes. We easily reproduced the field emission properties typically measured by others from multi-wall carbon nanotube arrays. Interestingly, we did this without having the helpful vertical alignment to enhance emission; our nanotubes were randomly oriented. The good emission was most likely possible due to the improved crystallinity, and therefore, electrical conductivity, of our nanotubes compared to those in the literature. However, toward the end of the project, we learned that while these 10-nm-diameter CNTs had superior crystalline structure to the work of others studying field emission from multi-wall CNT arrays, these nanotubes still

  16. Development of a Green Soft Chemical Method for the Synthesis of Cathode Materials Utilized in Lithium-ion Energy Storage Technologies

    NASA Astrophysics Data System (ADS)

    Wicker, Scott Ambrose

    The statement of the problem is to develop an environmental friendly, cost effective cathode material with the technical requirements to withstand the energy demand of directly storing electricity for the uses in today society. The author solved the problem by designing a water soluble, thermally stable organic moiety that is used as fuel and a template in the low temperature solution combustion synthesis of cathode materials utilized in lithium-ion energy storage devices. The Green Soft Chemical method (MADHAMS) is a useful alternative solution-combustion method for the synthesis of highly pure, fine-sized, spherical & cubic cathode powders. With the global demand pushing industrial applications toward green chemistry, we developed this technique with environmental friendly solvents. This MADHAMS method would fall within the "Self-Propagation Combustion Synthesis (SPCS)" family. SPCS is a family of methods that utilize metal nitrates as conventional oxidants and organic compounds as fuels. As the nitrate decomposes and the fuel is oxidized, energy is released into the local system as heat energy. The energy can be controlled by the metal-ion-to-fuel ratio. As part of this study, the properties and characteristics of the cathode powders prepared by a green soft chemical method are extensively investigated. This report also describes the non-isothermal investigation of the dependence of the activation energy on the extent of conversion of lithium cobalt dioxide using the iso-conversional method of Friedman. Lithium cobalt dioxide was prepared by the direct reaction of lithium carbonate and cobalt oxide. Cobalt oxide was prepared from the thermal decomposition of Cobalt (II) propenoate so that the starting materials used in the kinetic investigation would closely resemble or represent the natural decomposition products that are produced during the green soft chemical synthetic methods. The kinetic analysis of the variation in Ealpha with alpha revealed that this

  17. Solid-state cathode materials for lithium batteries: Effect of synthesis temperature on the physical and electrochemical properties of silver vanadium oxide

    SciTech Connect

    Leising, R.A.; Takeuchi, E.S. )

    1993-05-01

    Silver vanadium oxide (SVO, AgV[sub 2]O[sub 5.5]) was synthesized for use as a cathode material in lithium/SVO batteries. The material was prepared via a solid-state thermal reaction of silver nitrate and vanadium pentoxide in the presence of air. The surface morphology of the final product was found to be dependent on the temperature of synthesis of the material, as evidenced by SEM analysis of the samples. SVO synthesized at 320 and 375[degrees]C displayed irregularly shaped particles, while material prepared at 450[degrees]C was needlelike. SVO synthesized at 540[degrees]C appeared to be a mixture of large crystalline plates and irregular particles. All of the samples were analyzed by DSC, chemical analysis, X-ray powder diffraction, resistivity measurements, and constant-resistance discharge of Li/SVO test cells. The experimental capacities of the lower temperature materials (320,375[degrees]C) were similar to that found for SVO prepared at 450[degrees]C. A significant decrease in delivered capacity was noted when the SVO prepared at 540[degrees]C was used as a cathode material. 30 refs., 5 figs., 5 tabs.

  18. Pyrite (FeS2) nanocrystals as inexpensive high-performance lithium-ion cathode and sodium-ion anode materials.

    PubMed

    Walter, Marc; Zünd, Tanja; Kovalenko, Maksym V

    2015-05-28

    In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g(-1) and average energy density of 1237 Wh kg(-1) for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g(-1) for 400 cycles at a current rate of 1000 mA g(-1). In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides. PMID:25941034

  19. High energy cathode material

    SciTech Connect

    Li, Bin; Caldwell, Marissa; Tong, Wei; Kaye, Steven; Bhat, Vinay

    2015-09-01

    A composition for use in a battery electrode comprising a compound including lithium, manganese, nickel, and oxygen. The composition is characterized by a powder X-ray diffraction pattern having peaks including 18.6.+-.0.2, 35.0.+-.0.2, 36.4.+-.0.2, 37.7.+-.0.2, 42.1.+-.0.2, and 44.5.+-.0.2 degrees 2.theta. as measured using Cu K.sub..alpha. radiation.

  20. Effect of MWCNT on prepared cathode material (Li2Mn(x)Fe(1-x)SiO4) for energy storage applications

    NASA Astrophysics Data System (ADS)

    Agnihotri, Shruti; Rattan, Sangeeta; Sharma, A. L.

    2016-05-01

    The electrode material Li2MnFeSiO4 was successfully synthesized by standard sol-gel method and further modified with multiwalled carbon nano tube (MWCNT) to achieve better electrochemical properties. Our strategy helps us to improve the performance and storage capacity as compared with the bared material. This novel composite structure constructs an efficient cation (Li+) and electron channel which significantly enhance the Li+ ion diffusion coefficient and reduced charge transfer resistance. Hence leads to high conductivity and specific capacity. Characterization technique like Field emission scanning electron microscopy (FESEM) has been used to confirm its morphology, structure and particle size which comes out to be of the order of ˜20 to 30 nm. Lesser particle size reveals better electrochemical properties. Electrical conductivity (˜10-5 Scm-1) of MWCNT doped oxide cathode materials was recorded using ac impedance spectroscopy technique which reflects tenfold increment when compared with pure oxide cathode materials. Cyclic voltametery analysis has been done to calculate specific capacity and potential window of materials with and without CNTs. The results obtained from different techniques are well correlated and suitable for energy storage applications.

  1. The Na2FeP2O7-carbon nanotubes composite as high rate cathode material for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Longoni, Gianluca; Wang, Ji Eun; Jung, Young Hwa; Kim, Do Kyung; Mari, Claudio M.; Ruffo, Riccardo

    2016-01-01

    Among the viable positive electrode materials recently proposed for Na-ion secondary batteries, Na2FeP2O7 was investigated thanks to its facile preparation, the use of highly abundant and low cost raw materials, and the highest thermal stability among all others cathode materials. In the present work the electrochemical features of the Na2FeP2O7 are improved by synthesizing a Na2FeP2O7-carbon nanotubes composite with prominent high-rate performances. The material shows a reversible specific capacity of 86 mAh g-1 for 140 cycles at 1C and 68 mAh g-1 at 10C. An in depth investigation about the Na+ diffusion rates inside the material was conducted by electrochemical impedance spectroscopy.

  2. Influence of synthesis conditions on electrochemical properties of high-voltage Li 1.02Ni 0.5Mn 1.5O 4 spinel cathode material

    NASA Astrophysics Data System (ADS)

    Hwang, B. J.; Wu, Y. W.; Venkateswarlu, M.; Cheng, M. Y.; Santhanam, R.

    Li 1.02Ni 0.5Mn 1.5O 4 spinel cathode materials were successfully synthesized by a citric acid-assisted sol-gel method. The structure and morphology of the materials have been examined by X-ray diffraction and scanning electron microscopy, respectively. Electrochemical properties of the materials were investigated using cyclic voltammetry and galvanostatic charge/discharge measurements at two different temperatures (25 and 55 °C) using lithium anode. The initial capacity and capacity retention are highly dependent on the particle size, particle size distribution, crystallinity and purity of the materials. The Li 1.02Ni 0.5Mn 1.5O 4 materials synthesized both at 800 and 850 °C have shown best electrochemical performance in terms of capacity and capacity retention between 3.5 and 4.9 V with a LiPF 6 based electrolyte.

  3. Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte.

    PubMed

    Kim, Se Young; Lee, Ho-Taek; Kim, Kwang-Bum

    2013-12-14

    We employed graphene flakes as an air-cathode material for Li-O2 batteries and investigated their electrochemical properties in the dimethyl ether electrolyte. Graphene flakes were prepared by microwave-assisted reduction of graphene oxide, and their electrochemical properties were compared with those of Ketjen Black and carbon nanotubes. The catalytic effect of the prepared graphene flake-air cathode was demonstrated using cyclic voltammetry and discharge-charge testing performed under a limited discharge capacity. The catalytic effect of graphene flakes was also supported by morphological and spectroscopic analysis of the discharge-charge products formed on the graphene surface. Scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy revealed that Li2O2, Li2O, and Li2CO3 were the main discharge products on all carbon-air cathode surfaces. Raman spectroscopy revealed that LiRCO3 was additionally formed on Ketjen Black and carbon nanotubes during the first discharge; however, its formation was not observed on the graphene flakes. The catalytic effect of the graphene flakes and the absence of LiRCO3 in the discharge product could explain the higher Coulombic efficiency in the discharge-charge tests.

  4. Electrochemical properties of graphene flakes as an air cathode material for Li-O2 batteries in an ether-based electrolyte.

    PubMed

    Kim, Se Young; Lee, Ho-Taek; Kim, Kwang-Bum

    2013-12-14

    We employed graphene flakes as an air-cathode material for Li-O2 batteries and investigated their electrochemical properties in the dimethyl ether electrolyte. Graphene flakes were prepared by microwave-assisted reduction of graphene oxide, and their electrochemical properties were compared with those of Ketjen Black and carbon nanotubes. The catalytic effect of the prepared graphene flake-air cathode was demonstrated using cyclic voltammetry and discharge-charge testing performed under a limited discharge capacity. The catalytic effect of graphene flakes was also supported by morphological and spectroscopic analysis of the discharge-charge products formed on the graphene surface. Scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy revealed that Li2O2, Li2O, and Li2CO3 were the main discharge products on all carbon-air cathode surfaces. Raman spectroscopy revealed that LiRCO3 was additionally formed on Ketjen Black and carbon nanotubes during the first discharge; however, its formation was not observed on the graphene flakes. The catalytic effect of the graphene flakes and the absence of LiRCO3 in the discharge product could explain the higher Coulombic efficiency in the discharge-charge tests. PMID:24166701

  5. Structural changes and thermal stability of charged LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy

    DOE PAGES

    Bak, Seong -Min; Hu, Enyuan; Zhou, Yongning; Yu, Xiqian; Senanayake, Sanjaya D.; Cho, Sung -Jin; Kim, Kwang -Bum; Chung, Kyung Yoon; Yang, Xiao -Qing; Nam, Kyung -Wan

    2014-11-24

    Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygenmore » release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.« less

  6. Preparation and electrochemical performance of Pr2Ni0.6Cu0.4O4 cathode materials for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Yifang; Cheng, Jigui; Jiang, Qiumei; Yang, Junfang; Gao, Jianfeng

    2011-03-01

    Cathode material Pr2Ni0.6Cu0.4O4 (PNCO) for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is synthesized by a glycine-nitrate process using Pr6O11, NiO, and CuO powders as raw materials. X-ray diffraction analysis reveals that nanosized Pr2Ni0.6Cu0.4O4 powders with K2NiF4-type structure can be obtained from calcining the precursors at 1000 °C for 3 h. Scanning electron microscopy shows that the sintered PNCO samples have porous microstructure with a porosity of more than 30% and grain size smaller than 2 μm. A maximum conductivity of 130 S cm-1 is obtained from the PNCO samples sintered at 1050 °C. A single fuel cell based on the PNCO cathode with 30 μm Sm0.2Ce0.8O1.9 (SCO) electrolyte film and a 1 mm NiO-SCO anode support is constructed. The ohmic resistance of the single Ni-SCO/SCO/PNCO cell is 0.08 Ω cm2 and the area specific resistance (ASR) value is 0.19 Ω cm2 at 800 °C. Cell performance was also tested using humidified hydrogen (3% H2O) as fuel and air as oxidant. The single cell shows an open circuit voltage of 0.82 V and 0.75 V at 700 °C and 800 °C, respectively. Maximum power density is 238 mW cm-2 and 308 mW cm-2 at 700 °C and 800 °C, respectively. The preliminary tests have shown that Pr2Ni1-xCuxO4materials can be a good candidate for cathode materials of IT-SOFCs.

  7. Towards highly stable storage of sodium ions: a porous Na(3)V(2)(PO(4))(3)/C cathode material for sodium-ion batteries.

    PubMed

    Shen, Wei; Wang, Cong; Liu, Haimei; Yang, Wensheng

    2013-10-18

    A porous Na3 V2 (PO4 )3 cathode material coated uniformly with a layer of approximately 6 nm carbon has been synthesized by the sol-gel method combined with a freeze-drying process. The special porous morphology and structure significantly increases the specific surface area of the material, which greatly enlarges the contact area between the electrode and electrolyte, and consequently supplies more active sites for sodium ions. When employed as a cathode material of sodium-ion batteries, this porous Na3 V2 (PO4 )3 /C exhibits excellent rate performance and cycling stability; for instance, it shows quite a flat potential plateau at 3.4 V in the potential window of 2.7-4.0 V versus Na(+) /Na and delivers an initial capacity as high as 118.9 and 98.0 mA h g(-1) at current rates of 0.05 and 0.5 C, respectively, and after 50 cycles, a good capacity retention of 92.7 and 93.6 % are maintained. Moreover, even when the discharge current density is increased to 5 C (590 mA g(-1) ), an initial capacity of 97.6 mA h g(-1) can still be achieved, and an exciting capacity retention of 88.6 % is obtained after 100 cycles. The good cycle performance, excellent rate capability, and moreover, the low cost of Na3 V2 (PO4 )3 /C suggest that this material is a promising cathode for large-scale sodium-ion rechargeable batteries.

  8. Filtered cathodic arc source

    DOEpatents

    Falabella, S.; Sanders, D.M.

    1994-01-18

    A continuous, cathodic arc ion source coupled to a macro-particle filter capable of separation or elimination of macro-particles from the ion flux produced by cathodic arc discharge is described. The ion source employs an axial magnetic field on a cathode (target) having tapered sides to confine the arc, thereby providing high target material utilization. A bent magnetic field is used to guide the metal ions from the target to the part to be coated. The macro-particle filter consists of two straight solenoids, end to end, but placed at 45[degree] to one another, which prevents line-of-sight from the arc spot on the target to the parts to be coated, yet provides a path for ions and electrons to flow, and includes a series of baffles for trapping the macro-particles. 3 figures.

  9. Filtered cathodic arc source

    DOEpatents

    Falabella, Steven; Sanders, David M.

    1994-01-01

    A continuous, cathodic arc ion source coupled to a macro-particle filter capable of separation or elimination of macro-particles from the ion flux produced by cathodic arc discharge. The ion source employs an axial magnetic field on a cathode (target) having tapered sides to confine the arc, thereby providing high target material utilization. A bent magnetic field is used to guide the metal ions from the target to the part to be coated. The macro-particle filter consists of two straight solenoids, end to end, but placed at 45.degree. to one another, which prevents line-of-sight from the arc spot on the target to the parts to be coated, yet provides a path for ions and electrons to flow, and includes a series of baffles for trapping the macro-particles.

  10. Sepiolite-sulfur as a high-capacity, high-rate performance, and low-cost cathode material for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Pan, Junan; Wu, Cheng; Cheng, Juanjuan; Pan, Yong; Ma, Zengsheng; Xie, Shuhong; Li, Jiangyu

    2015-10-01

    Lithium-sulfur batteries have the theoretical energy density of up to 2600 Wh/kg, though its commercialization is limited by high material cost and poor cyclic performance. In this work, we show that sepiolite-sulfur is a high-capacity, high-rate performance, and low-cost cathode material for lithium-sulfur batteries. Sepiolite is a porous mineral with specific structure, outstanding physical and chemical adsorption characteristics, and excellent ion exchange capability, making it an ideal matrix material for lithium-sulfur batteries. It is shown that the first specific discharge capacity of sepiolite-sulfur cathode is about 1436 mAh g-1 at 0.2 C current rate, and it remains as high as 901 mAh g-1 after 300 cycles. Under 1 C current density, the first discharge capacity is 1206 mAh g-1, and maintains a high value of 601 mAh g-1 after 500 cycles. The raw materials are abundant and low cost, and the manufacturing process is simple and scalable, making it promising for the commercialization of lithium-sulfur batteries.

  11. Improved electrochemical properties of surface-coated Li(Ni,Co,Mn)0{sub 2} cathode material for Li secondary batteries.

    SciTech Connect

    Kang, S.-H.; Amine, K.; Chemical Engineering

    2006-01-01

    The surface of Li(Ni{sub 0.4}Co{sub 0.2}Mn{sub 0.4})O{sub 2} was coated with amorphous aluminum oxide using Al-isopropoxide. The effect of the surface coating on the cycling performance and high-temperature storage characteristics was investigated using coin-type cells. The surface-coated materials showed superior capacity retention at 55C as well as at room temperature and limited impedance rise during high-temperature storage compared with the uncoated material. From the a.c. impedance measurement, it was found that the uncoated material exhibited very large increase in the cathode/electrolyte interfacial impedance during cycling whereas the surface-coated materials showed a limited increase in the interfacial impedance.

  12. Bismuth and niobium co-doped barium cobalt oxide as a promising cathode material for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    He, Shaofei; Le, Shiru; Guan, Lili; Liu, Tao; Sun, Kening

    2015-11-01

    Perovskite oxides BaBi0.05Co0.95-yNbyO3-δ (BBCNy, 0 ≤ y ≤ 0.2) are synthesized and evaluated as potential cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). Highly charged Nb5+ successfully stabilizes the cubic perovskite structure to room temperature with Nb substituting content y ≥ 0.1. The phase structure, thermal expansion behavior, electrical conductivity and electrochemical performance of BBCNy with cubic phase are systematically studied. The samples exhibit excellent chemical compatibility with GDC and have sufficiently high electrical conductivities. However, the thermal expansion coefficients of BBCNy samples are nearly twice those of the most commonly used electrolyte materials YSZ and GDC, which is a major drawback for application in IT-SOFCs. The polarization resistances of BBCNy with y = 0.10, 0.15 and 0.20 on GDC electrolyte are 0.086, 0.079 and 0.107 Ω cm2 at 700 °C, respectively. Even though the YSZ electrolyte membrane and GDC barrier layer are approximately 50 μm and 10 μm in thickness, the highest maximum power density (1.23 W cm-2) of the single cell Ni-YSZ|YSZ|GDC|BBCN0.15 is obtained at 750 °C. Good long-term stability of the single cell with BBCN0.15 cathode is also demonstrated. These results demonstrate that BBCNy perovskite oxides with cubic structure are very promising cathode materials for IT-SOFCs.

  13. Enhanced rate performance of molybdenum-doped spinel LiNi0.5Mn1.5O4 cathode materials for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Yi, Ting-Feng; Chen, Bin; Zhu, Yan-Rong; Li, Xiao-Ya; Zhu, Rong-Sun

    2014-02-01

    The Mo-doped LiNi0.5Mn1.5O4 cathodes are successfully synthesized by citric acid-assisted sol-gel method. The result demonstrates that the Mo-doped LiMn1.4Ni0.55Mo0.05O4 cathodes present the improved electrochemical performance over pristine LiNi0.5Mn1.5O4. At the 2 C rate after 80 cycles, the discharge capacities are 68.5 mAh g-1 for the pristine LiNi0.5Mn1.5O4 material (53.9% of the capacity at 0.1 C), 107.4 mAh g-1 for the LiMn1.425Ni0.5Mo0.05O4 material (82.1% at 0.1 C), and 122.7 mAh g-1 for the LiMn1.4Ni0.55Mo0.05O4 material (90.5% at 0.1 C). Mo-doping is favorable for reducing the electrode polarization, suggesting that Mo-doped LiNi0.5Mn1.5O4 electrodes have faster lithium insertion/extraction kinetics during cycling. Mo-doped LiNi0.5Mn1.5O4 electrodes show lower charge-transfer resistance and higher lithium diffusion coefficients. In addition, LiMn1.4Ni0.55Mo0.05O4 cathode exhibits the smallest particle size, the lowest charge-transfer resistance and the highest lithium diffusion coefficient among all samples, indicating that it has a high reversibility and good rate capability.

  14. A facile approach to derive binder protective film on high voltage spinel cathode materials against high temperature degradation

    NASA Astrophysics Data System (ADS)

    Chou, Wei-Yu; Jin, Yi-Chun; Duh, Jenq-Gong; Lu, Cheng-Zhang; Liao, Shih-Chieh

    2015-11-01

    The electrochemical performance of spinel LiNi0.5Mn1.5O4 cathode combined with different binders at elevated temperature is firstly investigated. The water soluble binder, such as sodium carboxymethyl cellulose (CMC) and sodium alginate (SA), is compared with the polyvinylidene difluoride (PVdF) binder used in non-aqueous process. The aqueous process can meet the need of Li-ion battery industry due to environmental-friendly and cost effectiveness by replacing toxic organic solvent, such as N-methyl-pyrrolidone (NMP). In this study, a significantly improved high temperature cycling performance is successfully obtained as compared to the traditional PVdF binder. The aqueous binder can serve as a protective film which inhibits the serious Ni and Mn dissolution especially at elevated temperature. Our result demonstrates a facile approach to solve the problem of capacity fading for high voltage spinel cathodes.

  15. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E.; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

    2015-11-01

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

  16. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

    PubMed Central

    Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

    2015-01-01

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity. PMID:26593096

  17. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries.

    PubMed

    Hameed, A Shahul; Reddy, M V; Nagarathinam, M; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B V R; Vittal, Jagadese J

    2015-01-01

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity. PMID:26593096

  18. Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries.

    PubMed

    Hameed, A Shahul; Reddy, M V; Nagarathinam, M; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B V R; Vittal, Jagadese J

    2015-11-23

    Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

  19. Surface micro-structuring of intercalation cathode materials for lithium-ion batteries: a study of laser-assisted cone formation

    NASA Astrophysics Data System (ADS)

    Pfleging, W.; Smyrek, P.; Hund, J.; Bergfeldt, T.; Pröll, J.

    2015-03-01

    Strong efforts are currently undertaken in order to further improve the electrochemical performance of high energy lithium-ion batteries containing thick composite electrode materials. The properties of these electrode materials such as active surface area, film thickness, and film porosity strongly impact the cell life-time and cycling stability. A rather new approach is to generate hierarchical architectures into cathode materials by laser direct ablation as well as by laserassisted formation of self-organized structures. It could be shown that appropriate surface structures can lead to a significant improvement of lithium-ion diffusion kinetics leading to higher specific capacities at high charging and discharging currents. In this paper, the formation of self-organized conical structures in intercalation materials such as LiCoO2 and LiNi1/3Mn1/3Co1/3O2 is investigated in detail. For this purpose, the cathode materials are exposed to excimer laser radiation with wavelengths of 248 nm and 193 nm leading to cone structures with outer dimensions in the micrometer range. The process of cone formation is investigated using laser ablation inductively coupled plasma mass spectrometry and laser-induced breakdown spectroscopy (LIBS). Cone formation can be initiated for laser fluences up to 3 J/cm2 while selective removal of lithium was observed to be one of the key issues for starting the cone formation process. It could be shown that material re-deposition supports the cone-growth process leading to a low loss of active material. Besides the cone formation process, laser-induced chemical surface modification will be analysed by LIBS.

  20. Pyrite (FeS2) nanocrystals as inexpensive high-performance lithium-ion cathode and sodium-ion anode materials

    NASA Astrophysics Data System (ADS)

    Walter, Marc; Zünd, Tanja; Kovalenko, Maksym V.

    2015-05-01

    In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides.In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100

  1. Insight into the Atomic Structure of High-Voltage Spinel LiNi0.5Mn1.5O4 Cathode Material in the First Cycle

    DOE PAGES

    Huang, Xuejie; Yu, Xiqian; Lin, Mingxiang; Ben, Liubin; Sun, Yang; Wang, Hao; Yang, Zhenzhong; Gu, Lin; Yang, Xiao -Qing; Zhao, Haofei; et al

    2014-12-22

    Application of high-voltage spinel LiNi0.5Mn1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi0.5Mn1.5O4 cathode material. Although it is well-known that the structure of LiNi0.5Mn1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations ofmore » local atomic-level and average structure of LiNi0.5Mn1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi0.5Mn1.5O4//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi0.5Mn1.5O4 particles show migration of TM ions into tetrahedral Li sites to form a Mn3O4-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi0.5Mn1.5O4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi0.5Mn1.5O4 structure to obtain better electrochemical performance.« less

  2. Coating of α-MoO3 on nitrogen-doped carbon nanotubes by electrodeposition as a high-performance cathode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Liu, Xiaojiang; Wang, Ruilin; Mi, Rui; Li, Shaomin; Cui, Yanhua; Deng, Yafeng; Mei, Jun; Liu, Hao

    2015-01-01

    In this work, α-MoO3 nanoparticles are grown on the surface of nitrogen doped carbon nanotubes (N-CNTs) via a facile electrodeposition method. The morphology of as-prepared nanocomposite shows that the interconnected α-MoO3 nanoparticles are homogeneously distributed on the surface of N-CNTs. When investigated as a cathode material for lithium ion batteries, the nanocomposite reveals a high reversible discharge capacity of 250 mA h g-1 at a current density of 30 mA g-1, simultaneously with good cycling performance and excellent rate capability compared with pristine MoO3 powder. Kinetics of this process is investigated by electrochemical impedance spectroscopy to understand the difference in electrochemical performance and the interface properties between the α-MoO3/N-CNTs nanocomposite and pristine MoO3 powder electrode. The correlation between the unique structural features of α-MoO3/N-CNTs nanocomposite and its excellent electrochemical performance is also discussed. The excellent performance makes the as-prepared α-MoO3/N-CNTs nanocomposite a promising cathode material for high-performance lithium ion batteries.

  3. Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

    PubMed Central

    Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

    2015-01-01

    Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C. PMID:26065407

  4. Improving cycling performance of Li-rich layered cathode materials through combination of Al2O3-based surface modification and stepwise precycling

    NASA Astrophysics Data System (ADS)

    Kobayashi, Genki; Irii, Yuta; Matsumoto, Futoshi; Ito, Atsushi; Ohsawa, Yasuhiko; Yamamoto, Shinji; Cui, Yitao; Son, Jin-Young; Sato, Yuichi

    2016-01-01

    Controlling a cathode/electrolyte interface by modifying the surface of a cathode material with metal oxides or phosphates is a concept being explored as a possible strategy for improving the electrochemical performance of such materials. This study therefore looks at the crystal structure and chemical bonding state from bulk to surface of Al2O3-coated Li[Li0.2Ni0.18Co0.03Mn0.58]O2 and explores the influence that surface modification has on the electrochemical performance. Investigation by X-ray diffraction, hard X-ray photoelectron spectroscopy (HAXPES) and galvanostatic charge/discharge reaction reveals that the surface-modification layer is composed of Li-Al oxides and Al oxides, with a LiM1-xAlxO2 (M = transition metal) interlayer formed between the modification layer and Li[Li0.2Ni0.18Co0.03Mn0.58]O2 particles. The cycling performance of the Li-rich layered oxide is enhanced by its surface modification with Al2O3, achieving a discharge capacity of more than 310 mA h-1 and excellent cycling stability at 50 °C when combined with a more gradual Li-insertion/de-insertion process (i.e., stepwise precycling treatment).

  5. Synthesis, characterization and rate capability performance of the micro-porous MnO{sub 2} nanowires as cathode material in lithium batteries

    SciTech Connect

    R, Ranjusha; S, Sonia T.; S, Roshny; V, Lakshmi; Kalluri, Sujith; Kim, Taik Nam; Nair, Shantikumar V.; Balakrishnan, A.

    2015-10-15

    Graphical abstract: Translating MnO{sub 2} nanowires as cathode materials in coin cell and studying their discharge behavior and cycling stability at different C-rates. - Highlights: • MnO{sub 2} nanowires have been synthesized via hydrothermal route. • The nanowires were employed as cathode materials in Li-batteries. • Discharge and cycling stability were studied at different C-rates. • Specific capacity and power density of 251 mAh g{sup −1} and 200 W kg{sup −1} were attained. - Abstract: A peculiar architecture of one-dimensional MnO{sub 2} nanowires was synthesized by an optimized hydrothermal route and has been lucratively exploited to fabricate highly efficient microporous electrode overlays for lithium batteries. These fabricated electrodes comprised of interconnected nanoscale units with wire-shaped profile which exhibits high aspect ratio in the order of 10{sup 2}. Their outstanding intercalation/de-intercalation prerogatives have also been studied to fabricate lithium coin cells which revealed a significant specific capacity and power density of 251 mAh g{sup −1} and 200 W kg{sup −1}, respectively. A detailed electrochemical study was performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes influence the cyclic behavior of the electrode. Rate capability tests at different C-rates were performed to evaluate the capacity and cycling performance of these coin cells.

  6. Effect of Surfactants on the Physical Properties and Electrochemical Performance of LiFePO4 Cathode Material for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Vaishnava, P.; Naik, V. M.; Nazri, G. A.; Naik, R.

    2012-02-01

    The lithium iron phosphate chemistry is plagued by the poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, various research groups have adopted different strategies including decreasing the particle size, covering the particles with carbon, and adding dopants to the cathode material. Here, we report synthesis of C-LiFePO4 cathode materials using 0.25M lauric, myristic, and oleic acid as surfactants. The phase purity of all three C-LiFePO4 was confirmed by x-ray diffraction. SEM and TEM investigations reveal that the surfactants coat the LiFePO4 particles uniformly with carbon and the coating reduces the particle size to 20-30 nm. Due to high electrical conductivity, controlled particle size and suitable microstructure, among the three LiFePO4 coated samples, the sample with 0.25M lauric acid exhibited superior electrochemical performance in terms of specific capacity, the cycling stability and delivered high discharge capacity of 155, 150 and 123 mAhg-1 at 0.5 C, 1C and 5C, respectively. The correlation between the ratio of the intensities of the D and G bands observed by micro-Raman spectroscopy, conductivity and electrochemical characteristics will be presented.

  7. Determination of elemental constituents in different matrix materials and flow injection studies by the electrolyte cathode glow discharge technique with a new design

    SciTech Connect

    Shekhar, R.; Karunasagar, D.; Ranjit, M.; Arunachalam, J.

    2009-10-15

    An open-to-air type electrolyte cathode discharge (ELCAD) has been developed with a new design. The present configuration leads to a stable plasma even at low flow rates (0.96 mL/min). Plasma fluctuations arising from the variations in the gap between solid anode and liquid cathode were eliminated by providing a V-groove to the liquid glass-capillary. Cathode (ground) connection is given to the solution at the V-groove itself. Interfaced to atomic emission spectrometry (AES), its analytical performance is evaluated. The optimized molarity of the solution is 0.2 M. The analytical response curves for Ca, Cu, Cd, Pb, Hg, Fe, and Zn demonstrated good linearity. The limit of detections of Ca, Cu, Cd, Pb, Hg, Fe, and Zn are determined to be 17, 11, 5, 45, 15, 28, and 3 ng mL{sup -1}. At an integration time of 0.3 s, the relative standard deviation (RSD) values of the acid blank solutions are found to be less than 10% for the elements Ca, Cu, Cd, Hg, Fe, and Zn and 18% for Pb. The method is applied for the determination of the elemental constituents in different matrix materials such as tuna fish (IAEA-350), oyster tissue (NIST SRM 1566a), and coal fly ash (CFA SRM 1633b). The obtained results are in good agreement with the certified values. The accuracy is found to be between 7% and 0.6% for major to trace levels of constituent elements and the precision between 11% and 0.6%. For the injection of 100 {mu} L of 200 ng mL{sup -1} mercury solution at the flow rate of 0.8 mL/min, the flow injection studies resulted in the relative standard deviation (RSD) of 8%, concentration detection limit of 10 ng/mL, and mass detection limit of 1 ng for mercury.

  8. Determination of elemental constituents in different matrix materials and flow injection studies by the electrolyte cathode glow discharge technique with a new design.

    PubMed

    Shekhar, R; Karunasagar, D; Ranjit, Manjusha; Arunachalam, J

    2009-10-01

    An open-to-air type electrolyte cathode discharge (ELCAD) has been developed with a new design. The present configuration leads to a stable plasma even at low flow rates (0.96 mL/min). Plasma fluctuations arising from the variations in the gap between solid anode and liquid cathode were eliminated by providing a V-groove to the liquid glass-capillary. Cathode (ground) connection is given to the solution at the V-groove itself. Interfaced to atomic emission spectrometry (AES), its analytical performance is evaluated. The optimized molarity of the solution is 0.2 M. The analytical response curves for Ca, Cu, Cd, Pb, Hg, Fe, and Zn demonstrated good linearity. The limit of detections of Ca, Cu, Cd, Pb, Hg, Fe, and Zn are determined to be 17, 11, 5, 45, 15, 28, and 3 ng mL(-1). At an integration time of 0.3 s, the relative standard deviation (RSD) values of the acid blank solutions are found to be less than 10% for the elements Ca, Cu, Cd, Hg, Fe, and Zn and 18% for Pb. The method is applied for the determination of the elemental constituents in different matrix materials such as tuna fish (IAEA-350), oyster tissue (NIST SRM 1566a), and coal fly ash (CFA SRM 1633b). The obtained results are in good agreement with the certified values. The accuracy is found to be between 7% and 0.6% for major to trace levels of constituent elements and the precision between 11% and 0.6%. For the injection of 100 microL of 200 ng mL(-1) mercury solution at the flow rate of 0.8 mL/min, the flow injection studies resulted in the relative standard deviation (RSD) of 8%, concentration detection limit of 10 ng/mL, and mass detection limit of 1 ng for mercury. PMID:19715301

  9. High current density cathode for electrorefining in molten electrolyte

    DOEpatents

    Li, Shelly X.

    2010-06-29

    A high current density cathode for electrorefining in a molten electrolyte for the continuous production and collection of loose dendritic or powdery deposits. The high current density cathode eliminates the requirement for mechanical scraping and electrochemical stripping of the deposits from the cathode in an anode/cathode module. The high current density cathode comprises a perforated electrical insulated material coating such that the current density is up to 3 A/cm.sup.2.

  10. Low voltage cathodic protection for high strength steels. Part 1: Definition of a new aluminum galvanic anode material

    SciTech Connect

    Pautasso, J.P.; Le Guyader, H.; Debout, V.

    1998-12-31

    Zn or Al-Zn-In sacrificial anodes are commonly used to protect submerged marine structures from general corrosion and galvanic corrosion. However, such electronegative alloys can also induce stress corrosion cracking or hydrogen embrittlement on high strength steels. Decreasing the electronegative potential applied to the structure, in the suitable range (around {minus}0.80 V vs Ag/AgCl) can significantly reduce the amount of hydrogen produced by the cathodic reaction and thus limit the risk of hydrogen embrittlement. The present work has consisted in determining the criteria for a new cathodic protection system with low voltage anodes and selecting one anode that matches the determined requirements, on the basis of laboratory tests. Among the various alloys tested the Al-O.1% Ga anode provided the most promising results and therefore was selected. The first full scale marine tests performed on an industrial casting of this anode have shown the effectiveness of the Al-O.1% Ga anode in the chosen potential range, with a satisfactory galvanic efficiency in real environments.

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

    SciTech Connect

    Lee, Young Joo; Wang, Francis; Grey, Clare P.; Mukerjee, Sanjeev; McBreen, James

    1998-11-30

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

  12. A pulsed cathodic arc spacecraft propulsion system

    NASA Astrophysics Data System (ADS)

    Neumann, P. R. C.; Bilek, M. M. M.; Tarrant, R. N.; McKenzie, D. R.

    2009-11-01

    We investigate the use of a centre-triggered cathodic arc as a spacecraft propulsion system that uses an inert solid as a source of plasma. The cathodic vacuum arc produces almost fully ionized plasma with a high exhaust velocity (>104 m s-1), giving a specific impulse competitive with other plasma or ion thrusters. A centre trigger design is employed that enables efficient use of cathode material and a high pulse-to-pulse repeatability. We compare three anode geometries, two pulse current profiles and two pulse durations for their effects on impulse generation, energy and cathode material usage efficiency. Impulse measurement is achieved through the use of a free-swinging pendulum target constructed from a polymer material. Measurements show that impulse is accurately controlled by varying cathode current. The cylindrical anode gave the highest energy efficiency. Cathode usage is optimized by choosing a sawtooth current profile. There is no requirement for an exhaust charge neutralization system.

  13. Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material

    SciTech Connect

    Rumble, C.; Conry, T.E.; Doeff, Marca; Cairns, Elton J.; Penner-Hahn, James E.; Deb, Aniruddha

    2010-06-14

    Li(Ni{sub 0.4}Co{sub 0.15}Al{sub 0.05}Mn{sub 0.4})O{sub 2} was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. In situ X-ray absorption spectroscopy (XAS) was performed, utilizing a novel in situ electrochemical cell, specifically designed for long-term X-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range. (1.0-4.7 V) XAS measurements were performed at different states of charge (SOC) during cycling, at the Ni, Co, and the Mn edges, revealing details about the response of the cathode to Li insertion and extraction processes. The extended X-ray absorption fine structure (EXAFS) region of the spectra revealed the changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the SOC of the material. The oxidation states of the transition metals in the system are Ni{sup 2+}, Co{sup 3+}, and Mn{sup 4+} in the as-made material (fully discharged), while during charging the Ni{sup 2+} is oxidized to Ni{sup 4+} through an intermediate stage of Ni{sup 3+}, Co{sup 3+} is oxidized toward Co{sup 4+}, and Mn was found to be electrochemically inactive and remained as Mn{sup 4+}. The EXAFS results during cycling show that the Ni-O changes the most, followed by Co-O, and Mn-O varies the least. These measurements on this cathode material confirmed that the material retains its symmetry and good structural short-range order leading to the superior cycling reported earlier.

  14. Structural and Electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material

    SciTech Connect

    Rumble, C.; Conry, T.E.; Doeff, Marca; Cairns, Elton J.; Penner-Hahn, James. E.; Deb, Aniruddha

    2010-02-02

    Li(Ni{sub 0.4}Co{sub 0.2-y}Al{sub y}Mn{sub 0.4})O{sub 2} with y=0.05 was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. The effect of the substitution was studied by in-situ X-ray absorption spectroscopy (XAS), utilizing a novel in situ electrochemical cell, specifically designed for long-term X-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range (1.0-4.7 V). XAS measurements were performed at different states-of-charge (SOC) during cycling, at the Ni, Co, and the Mn edges, revealing details about the response of the cathode to Li insertion and extraction processes. The extended X-ray absorption fine structure region of the spectra revealed the changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the SOC of the material. The oxidation states of the transition metals in the system are Ni{sup 2+}, Co{sup 3+}, and Mn{sup 4+} in the as-made material (fully discharged), while during charging the Ni{sup 2+} is oxidized to Ni{sup 4+} through an intermediate stage of Ni{sup 3+}, Co{sup 3+} is oxidized towards Co{sup 4+} and Mn was found to be electrochemically inactive and remains as Mn{sup 4+}. The EXAFS results during cycling show that the Ni-O changes the most, followed by Co-O and Mn-O varies the least. These measurements on this cathode material confirmed that the material retains its symmetry and good structural short-range order leading to the superior cycling reported earlier.

  15. Investigating the reversibility of structural modifications of LixNiyMnzCo1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

    SciTech Connect

    Hwang, Sooyeon; Bak, Seong -Min; Kim, Seung Min; Chung, Kyung Yoon; Chang, Wonyoung

    2015-08-11

    In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of LixNiyMnzCo1-y-zO₂ (NMC; y, z = 0.8, 0.1 and 0.4, 0.3, respectively) cathode materials during the initial charge/discharge. Various analytical tools, such as X-ray diffraction, selected-area electron diffraction, electron energy-loss spectroscopy, and high-resolution electron microscopy, are used to examine the structural properties of the NMC cathode materials at the three different scales. Cut-off voltages of 4.3 and 4.8 V are applied during the electrochemical tests as the normal and extreme conditions, respectively. The high-Ni-content NMC cathode materials exhibit unusual behaviors, which is deviate from the general redox reactions during the charge or discharge. The transition metal (TM) ions in the high-Ni-content NMC cathode materials, which are mostly Ni ions, are reduced at 4.8 V, even though TMs are usually oxidized to maintain charge neutrality upon the removal of Li. It was found that any changes in the crystallographic and electronic structures are mostly reversible down to the sub-surface scale, despite the unexpected reduction of Ni ions. However, after the discharge, traces of the phase transitions remain at the edges of the NMC cathode materials at the scale of a few nanometers (i.e., surface scale). This study demonstrates that the structural modifications in NMC cathode materials are induced by charge as well as discharge at multiple length scales. These changes are nearly reversible after the first cycle, except at the edges of the samples, which should be avoided because these highly localized changes can initiate battery degradation.

  16. Controlled solvothermal synthesis and electrochemical performance of LiCoPO4 submicron single crystals as a cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wu, Borong; Xu, Hongliang; Mu, Daobin; Shi, Lili; Jiang, Bing; Gai, Liang; Wang, Lei; Liu, Qi; Ben, Liubin; Wu, Feng

    2016-02-01

    The submicron single crystals of LiCoPO4 with 500 nm diameter are prepared by solvothermal method. The carbon coated sample is obtained using sucrose as carbon source under 650 °C subsequently. It is investigated that the solvent composition has an effect on the morphology and the electrochemical performance of the cathode material. The as-prepared samples are characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopic, dynamic light scattering, and Fourier transform infrared spectra. The electrochemical performance is evaluated by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The LiCoPO4/C cathode can reach an initial discharge capacity of 123.8 mA h g-1 at 0.1C, with a retention of 83% after 100 cycles. A discharge capacity of 84.9 mA h g-1 is still attainable when the rate is up to 2C. The good cycling performance and rate capability are contributed to the decrease of particle size along with the lower antisite defect concentration in the LCP crystals, and uniform carbon coating.

  17. Highly Crystallized Na₂CoFe(CN)₆ with Suppressed Lattice Defects as Superior Cathode Material for Sodium-Ion Batteries.

    PubMed

    Wu, Xianyong; Wu, Chenghao; Wei, Congxiao; Hu, Ling; Qian, Jiangfeng; Cao, Yuliang; Ai, Xinping; Wang, Jiulin; Yang, Hanxi

    2016-03-01

    Prussian blue and its analogues have received particular attention as superior cathodes for Na-ion batteries due to their potential 2-Na storage capacity (∼170 mAh g(-1)) and low cost. However, most of the Prussian blue compounds obtained from the conventional synthetic routes contain large amounts of Fe(CN)6 vacancies and coordinated water molecules, which leads to the collapse of cyano-bridged framework and serious deterioration of their Na-storage ability. Herein, we propose a facile citrate-assisted controlled crystallization method to obtain low-defect Prussian blue lattice with greatly improved Na-storage capacity and cycling stability. As an example, the as-prepared Na2CoFe(CN)6 nanocrystals demonstrate a reversible 2-Na storage reaction with a high specific capacity of 150 mAh g(-1) and a ∼ 90% capacity retention over 200 cycles, possibly serving as a low cost and high performance cathode for Na-ion batteries. In particular, the synthetic strategy described in this work may be extended to other coordination-framework materials for a wide range of energy conversion and storage applications.

  18. Budding willow branches shaped Na3V2(PO4)3/C nanofibers synthesized via an electrospinning technique and used as cathode material for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Hui; Bai, Ying; Wu, Feng; Li, Yu; Wu, Chuan

    2015-01-01

    Budding willow branches shaped Na3V2(PO4)3/C nanofibers were successfully synthesized by a simple electrospinning technique with Poly(vinyl pyrrilidone) (PVP). The Na3V2(PO4)3/C nanoparticles that anchored on the nanofibers surface seemed like the willow buds; the inner core of the nanofibers, which composed Na3V2(PO4)3, looked like willow twig and the uniform carbon layer was same with willow bark. Such special morphology played a vital role in improving cycle stability and rate capability of the electrode due to the conductive network built up by nanofibers. The Na3V2(PO4)3/C nanofibers cathode exhibited an initial specific capacity of 106.8 mAh g-1 at a current density of 0.2C, still stabling at 107.2 mAh g-1 after 125 cycles with excellent cycle stability. Moreover, a capacity retention of 95.7% was obtained when Na3V2(PO4)3/C nanofibers cycled stepwise from 0.2 to 2C. Good electrochemical performance should be ascribed to both the special morphology and preferential growth of the (113) plane. The simple synthesis technique and good electrochemical performance suggests that this material with the special shape of budding willow branches is a promising cathode for sodium ion batteries.

  19. Bicontinuous Structure of Li₃V₂(PO₄)₃ Clustered via Carbon Nanofiber as High-Performance Cathode Material of Li-Ion Batteries.

    PubMed

    Chen, Lin; Yan, Bo; Xu, Jing; Wang, Chunguang; Chao, Yimin; Jiang, Xuefan; Yang, Gang

    2015-07-01

    In this work, the composite structure of Li3V2(PO4)3 (LVP) nanoparticles with carbon nanofibers (CNF) is designed. The size and location of LVP particles, and the degree of graphitization and diameter of carbon nanofibers, are optimized by electrospinning and heat treatment. The bicontinuous morphologies of LVP/CNF are dependent on the carbonization of PVP and simultaneous growing of LVP, with the fibers shrunk and the LVP crystals grown toward the outside. LVP nanocystals clustered via carbon nanofibers guarantee improving the diffusion ability of Li(+), and the carbon fiber simultaneously guarantees the effective electron conductivity. Compared with the simple carbon-coated LVP and pure LVP, the particle-clustered structure guarantees high rate capability and long-life cycling stability of NF-LVP as cathode for LIBs. At 20 C rate in the range 3.0-4.3 V, NF-LVP delivers the initial capacity of 122.6 mAh g(-1) close to the theoretical value of 133 mAh g(-1), and maintains 97% of the initial capacity at the 1000th cycle. The bead-like structure of cathode material clustered via carbon nanofibers via electrospinning will be further applied to high-performance LIBs.

  20. Activated carbons derived from coconut shells as high energy density cathode material for Li-ion capacitors

    NASA Astrophysics Data System (ADS)

    Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Kumar, Palaniswamy Suresh; Balasubramanian, Rajasekhar; Ramakrishna, Seeram; Madhavi, Srinivasan; Srinivasan, M. P.

    2013-10-01

    In this manuscript, a dramatic increase in the energy density of ~ 69 Wh kg-1 and an extraordinary cycleability ~ 2000 cycles of the Li-ion hybrid electrochemical capacitors (Li-HEC) is achieved by employing tailored activated carbon (AC) of ~ 60% mesoporosity derived from coconut shells (CS). The AC is obtained by both physical and chemical hydrothermal carbonization activation process, and compared to the commercial AC powders (CAC) in terms of the supercapacitance performance in single electrode configuration vs. Li. The Li-HEC is fabricated with commercially available Li4Ti5O12 anode and the coconut shell derived AC as cathode in non-aqueous medium. The present research provides a new routine for the development of high energy density Li-HEC that employs a mesoporous carbonaceous electrode derived from bio-mass precursors.

  1. Activated carbons derived from coconut shells as high energy density cathode material for Li-ion capacitors

    PubMed Central

    Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Kumar, Palaniswamy Suresh; Balasubramanian, Rajasekhar; Ramakrishna, Seeram; Madhavi, Srinivasan; Srinivasan, M. P.

    2013-01-01

    In this manuscript, a dramatic increase in the energy density of ~ 69 Wh kg−1 and an extraordinary cycleability ~ 2000 cycles of the Li-ion hybrid electrochemical capacitors (Li-HEC) is achieved by employing tailored activated carbon (AC) of ~ 60% mesoporosity derived from coconut shells (CS). The AC is obtained by both physical and chemical hydrothermal carbonization activation process, and compared to the commercial AC powders (CAC) in terms of the supercapacitance performance in single electrode configuration vs. Li. The Li-HEC is fabricated with commercially available Li4Ti5O12 anode and the coconut shell derived AC as cathode in non-aqueous medium. The present research provides a new routine for the development of high energy density Li-HEC that employs a mesoporous carbonaceous electrode derived from bio-mass precursors. PMID:24141527

  2. Activated carbons derived from coconut shells as high energy density cathode material for Li-ion capacitors.

    PubMed

    Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Kumar, Palaniswamy Suresh; Balasubramanian, Rajasekhar; Ramakrishna, Seeram; Madhavi, Srinivasan; Srinivasan, M P

    2013-10-21

    In this manuscript, a dramatic increase in the energy density of ~ 69 Wh kg⁻¹ and an extraordinary cycleability ~ 2000 cycles of the Li-ion hybrid electrochemical capacitors (Li-HEC) is achieved by employing tailored activated carbon (AC) of ~ 60% mesoporosity derived from coconut shells (CS). The AC is obtained by both physical and chemical hydrothermal carbonization activation process, and compared to the commercial AC powders (CAC) in terms of the supercapacitance performance in single electrode configuration vs. Li. The Li-HEC is fabricated with commercially available Li₄Ti₅O₁₂ anode and the coconut shell derived AC as cathode in non-aqueous medium. The present research provides a new routine for the development of high energy density Li-HEC that employs a mesoporous carbonaceous electrode derived from bio-mass precursors.

  3. Development of High Energy Cathode (PNNL)

    SciTech Connect

    Zhang, Jiguang; Liu, Jun

    2011-01-01

    Lithium ion batteries with high energy densities are required to reach DOE’s goal on early commercialization of electrical vehicles, including HEV, PHEV and EV. To increase the energy of cathode, voltage or/and capacity of cathode need to be increased. During FY10, we have investigated cathode materials with high operation voltages, for example LiMnPO4, and renewable organic cathode with high capacities. Environmentally friendly materials and low cost synthesis approaches have been intentionally explored during our efforts.

  4. Improved 4-chlorophenol dechlorination at biocathode in bioelectrochemical system using optimized modular cathode design with composite stainless steel and carbon-based materials.

    PubMed

    Kong, Fanying; Wang, Aijie; Ren, Hong-Yu

    2014-08-01

    This study developed and optimized a modular biocathode materials design in bioelectrochemical system (BES) using composite metal and carbon-based materials. The 4-chlorophenol (4-CP) dechlorination could be improved with such composite materials. Results showed that stainless steel basket (SSB) filled with graphite granules (GG) and carbon brush (CB) (SSB/GG/CB) was optimum for dechlorination, followed by SSB/CB and SSB/GG, with rate constant k of 0.0418 ± 0.0002, 0.0374 ± 0.0004, and 0.0239 ± 0.0002 h(-1), respectively. Electrochemical impedance spectroscopy (EIS) demonstrated that the composite materials with metal can benefit the electron transfer and decrease the charge transfer resistance to be 80.4 Ω in BES-SSB/GG/CB, much lower than that in BES-SSB (1674.3 Ω), BES-GG (387.3 Ω), and BES-CB (193.8 Ω). This modular cathode design would be scalable with successive modules for BES scale-up, and may offer useful information to guide the selection and design of BES materials towards dechlorination improvement in wastewater treatment. PMID:24926596

  5. Preparation and Electrochemical Properties of Coral-like Li2FeSiO4/C Cathode Material by Two-Step Precipitation Method

    NASA Astrophysics Data System (ADS)

    Yan, Yinglin; Ren, Bing; Xu, Yunhua; Wang, Juan; Yang, Rong; Zhong, Lisheng; Zhao, Nana; Wu, Hong

    2016-06-01

    Lithium iron silicate (Li2FeSiO4) cathode materials have been synthesized by a soft chemical method combined with spray drying, being both simple and economical. Super P, as a new kind of nanoscale carbon black, was added in the synthesis process. The phase and microstructure of the samples were characterized by x-ray diffraction analysis, scanning electron microscopy, and transmission electron microscopy. The results show that the obtained Li2FeSiO4 possessed coral-like morphology with size range from 250 nm to 450 nm. Super P was decorated on the surface of the Li2FeSiO4 particles. Furthermore, the electrochemical properties of the products were tested, indicating that the as-obtained Li2FeSiO4/C composite presented high specific discharge capacities and stable cycling performance, which can be attributed to the coral-like morphology and Super P coating.

  6. Preparation and Electrochemical Properties of Coral-like Li2FeSiO4/C Cathode Material by Two-Step Precipitation Method

    NASA Astrophysics Data System (ADS)

    Yan, Yinglin; Ren, Bing; Xu, Yunhua; Wang, Juan; Yang, Rong; Zhong, Lisheng; Zhao, Nana; Wu, Hong

    2016-10-01

    Lithium iron silicate (Li2FeSiO4) cathode materials have been synthesized by a soft chemical method combined with spray drying, being both simple and economical. Super P, as a new kind of nanoscale carbon black, was added in the synthesis process. The phase and microstructure of the samples were characterized by x-ray diffraction analysis, scanning electron microscopy, and transmission electron microscopy. The results show that the obtained Li2FeSiO4 possessed coral-like morphology with size range from 250 nm to 450 nm. Super P was decorated on the surface of the Li2FeSiO4 particles. Furthermore, the electrochemical properties of the products were tested, indicating that the as-obtained Li2FeSiO4/C composite presented high specific discharge capacities and stable cycling performance, which can be attributed to the coral-like morphology and Super P coating.

  7. Encapsulation of LiFePO4 by in-situ graphitized carbon cage towards enhanced low temperature performance as cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yao, Bin; Ding, Zhaojun; Zhang, Jianxin; Feng, Xiaoyu; Yin, Longwei

    2014-08-01

    The severe capacity decay of LiFePO4 at low temperatures (≤0 °C) limits its wide applications as cathode materials for energy storage batteries. Creating comprehensive carbon network between particles with improved electronic conductivity is a well known solution to this problem. Here, a novel structured LiFePO4/C composite was prepared by a facile solid state route, in which nanosized LiFePO4 spheres were encapsulated by in-situ graphitized carbon cages. With the enhancement in electronic conductivity (2.15e-1 S cm-1), the composite presented excellent rate performance at room temperature and remarkable capacity retention at -40 °C, with charge transfer resistance much lower than commercial LiFePO4.

  8. Key strategies for enhancing the cycling stability and rate capacity of LiNi0.5Mn1.5O4 as high-voltage cathode materials for high power lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yi, Ting-Feng; Mei, Jie; Zhu, Yan-Rong

    2016-06-01

    Spinel LiNi0.5Mn1.5O4 (LNMO) is one of the most promising high voltage cathode materials for future application due to its advantages of large reversible capacity, high thermal stability, low cost, environmental friendliness, and high energy density. LNMO can provide 20% and 30% higher energy density than traditional cathode materials LiCoO2 and LiFePO4, respectively. Unfortunately, LNMO-based batteries with LiPF6-based carbonate electrolytes always suffer from severe capacity deterioration and poor thermostability because of the oxidization of organic carbonate solvents and decomposition of LiPF6, especially at elevated temperatures and water-containing environment. Hence, it is necessary to systematically and comprehensively summarize the progress in understanding and modifying LNMO cathode from various aspects. In this review, the structure, transport properties and different reported possible fading mechanisms of LNMO cathode are first discussed detailedly. And then, the major goal of this review is to highlight new progress in using proposed strategies to improve the cycling stability and rate capacity of LNMO-based batteries, including synthesis, control of special morphologies, element doping and surface coating etc., especially at elevated temperatures. Finally, an insight into the future research and further development of LNMO cathode is discussed.

  9. Interrelationship between marine biofouling and cathodic protection

    SciTech Connect

    Little, B.J.; Wagner, P.A. )

    1993-09-01

    Microorganisms colonize and form a gelatinous biofilm on all engineering materials exposed in natural marine environments, including cathodically protected surfaces. The impact of cathodic protection (CP) potentials on the chemical/biological composition of the biofilm and the impact of the biofilms on potentials required for CP have been the subject of many recent investigations. Literature on these subjects will be reviewed with emphasis on clarifying interactions between living and nonliving deposits on cathodically protected metal surfaces.

  10. Enhanced electrochemical performance of LiFe0.6Mn0.4PO4/C cathode material prepared by ferrocene-assisted calcination process

    NASA Astrophysics Data System (ADS)

    Yang, Xinhe; Mi, Yingying; Zhang, Weidong; Wu, Borong; Zhou, Henghui

    2015-02-01

    A ferrocene-assisted calcination process (FACP) has been applied during the preparation of LiFe0.6Mn0.4PO4/C cathode material. Ferrocene works as a promoter to improve the quality of the coated carbon layers. The influence of ferrocene on the property of carbon layers and electrochemical performance of LiFe0.6Mn0.4PO4/C has been investigated systematically. The LiFe0.6Mn0.4PO4/C with FACP presents more uniformly and tightly coated carbon layers with higher graphitization degree than the sample without FACP. High-quality carbon layers can greatly enhance the electrochemical performance of cathode materials. The LiFe0.6Mn0.4PO4/C with FACP behaves higher discharge capacities (163.6 and 120.7 mAh g-1 at 0.2C and 20C, respectively) than the LiFe0.6Mn0.4PO4/C without FACP (158.4 and 111.5 mAh g-1 at the same rates). Furthermore, the LiFe0.6Mn0.4PO4/C with FACP exhibits excellent cycling performance even at 60 °C, still delivering capacity retention above 96% after 100 cycles at 3C, while the retention of the controlled sample is only 70% after 75 cycles. The cycling performance of the LiFe0.6Mn0.4PO4/C with FACP at high temperature is largely improved.

  11. Template-Engaged Synthesis of 1D Hierarchical Chainlike LiCoO2 Cathode Materials with Enhanced High-Voltage Lithium Storage Capabilities.

    PubMed

    Wu, Naiteng; Zhang, Yun; Wei, Yunhong; Liu, Heng; Wu, Hao

    2016-09-28

    A novel 1D hierarchical chainlike LiCoO2 organized by flake-shaped primary particles is synthesized via a facile template-engaged strategy by using CoC2O4·2H2O as a self-sacrificial template obtained from a simple coprecipitation method. The resultant LiCoO2 has a well-built hierarchical structure, consisting of secondary micrometer-sized chains and sub-micrometer-sized primary flakes, while these primary LiCoO2 flakes have specifically exposed fast-Li(+)-diffused active {010} facets. Owing to this unique hierarchical structure, the chainlike LiCoO2 serves as a stable cathode material for lithium-ion batteries (LIBs) operated at a high cutoff voltage up to 4.5 V, enabling highly reversible capacity, remarkable rate performance, and long-term cycle life. Specifically, the chainlike LiCoO2 can deliver a reversible discharge capacity as high as 168, 156, 150, and 120 mAh g(-1) under the current density of 0.1, 0.5, 1, and 5 C, respectively, while about 85% retention of the initial capacity can be retained after 200 cycles under 1 C at room temperature. Moreover, the chainlike LiCoO2 also shows an excellent cycling stability at a wide operating temperature range, showing the capacity retention of ∼73% after 200 cycles at 55 °C and of ∼68% after 50 cycles at -10 °C, respectively. The work described here suggests the great potential of the hierarchical chainlike LiCoO2 as high-voltage cathode materials aimed toward developing advanced LIBs with high energy density and power density.

  12. Local structural changes in LiMn1.5Ni0.5O4 spinel cathode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Rana, Jatinkumar; Glatthaar, Sven; Gesswein, Holger; Sharma, Neeraj; Binder, Joachim R.; Chernikov, Roman; Schumacher, Gerhard; Banhart, John

    2014-06-01

    Local structural changes in LiMn1.5Ni0.5O4 cathode material were investigated by X-ray absorption spectroscopy in-operando using a specially designed electrochemical cell. The average structure of the starting material determined by neutron powder diffraction confirmed partial ordering of Mn and Ni cations on the octahedral sites in the spinel structure. It is observed that the electrochemical activity of the material between 3.5 V and 5.0 V is largely attributed to a two-step Ni2+/Ni4+ redox reaction. However, a small fraction of Mn3+ present in the pristine material also participates in electrochemical processes via a Mn3+/Mn4+ redox reaction. The excess lithium inserted into the material during deep discharge of the cell down to 2.0 V causes a further reduction of Mn4+ to Mn3+, while Ni remains electrochemically inactive. An increased proportion of Mn3+ in the material increases the distortion of MnO6 octahedra by the Jahn-Teller effect, which locally reduces the crystal symmetry from cubic to tetragonal, giving rise to the formation of domains of a Li2Mn2O4-type tetragonal phase. The fraction of this tetragonal phase was found to be directly related to the excess lithium inserted into the material. Upon subsequent charging to 2.9 V, the tetragonal phase tends to revert back to the original cubic spinel phase. The observed decline in the electrochemical performance of the material when cycled between 2.0 V and 5.0 V may be attributed to repetitive structural changes associated with the cubic ↔ tetragonal phase transition.

  13. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4. PMID:26548581

  14. Electrochemical Kinetics and Performance of Layered Composite Cathode Material Li[Li0.2Ni0.2Mn0.6]O2

    SciTech Connect

    Zheng, Jianming; Shi, Wei; Gu, Meng; Xiao, Jie; Zuo, Pengjian; Wang, Chong M.; Zhang, Jiguang

    2013-10-10

    Lithium-rich, manganese-rich (LMR) layered composite cathode material Li[Li0.2Ni0.2Mn0.6]O2 has been successfully prepared by a co-precipitation method and its structure is confirmed by XRD characterization. The material delivers a high discharge capacity of 281 mAh g-1, when charged and discharged at a low current density of 10 mA g-1. However, significant increase of cell polarization and decrease of discharge capacity are observed at voltages below 3.5 V with increasing current densities. Galvanostatic intermittent titration technique (GITT) analysis demonstrates that lithium ion intercalation/de-intercalation reactions in this material are kinetically controlled by Li2MnO3 and its activated MnO2 component. The relationship between the electrochemical kinetics and rate performance as well as cycling stability has been systematically investigated. High discharge capacity of 149 mAh g-1 can be achieved at 10 C charge rate and C/10 discharge rate. The result demonstrates that the Li2MnO3 based material could withstand high charge rate (except initial activation process), which is very promising for practical applications. A lower discharge current density is preferred to overcome the kinetic barrier of lithium ion intercalation into MnO2 component, in order to achieve higher discharge capacity even at high charge rates.

  15. Quaternary phase diagrams of spinel Liy□1-yMnxNi2 -xO4 and composite cathode voltages for concentration gradient materials

    NASA Astrophysics Data System (ADS)

    Hao, Shiqiang; Lu, Zhi; Wolverton, Christopher

    2016-07-01

    Core-shell coating structures and concentration gradient materials may enhance Li-ion battery performance by integrating advantages of core and shell components without introducing unfavorable problems associated with general coatings. The fundamental thermodynamic properties of concentration gradient composite materials are complex due to the multicomponent nature of the problem. We systematically study the thermodynamics of ordering and phase separation in the quaternary spinel Liy□1-yMnxNi2 -xO4 (□ means vacancy) system by density functional theory calculations, together with the coupled cluster expansion method with interactions within and between (Li/□) and (Mn/Ni) sublattices. On the basis of coupled cluster expansion interactions and Monte Carlo simulations, we calculate quaternary phase diagrams as a function of temperature as well as voltage profiles of single ordered phases and multiphase composite structures. The phase diagram and voltage results are in good agreement with available experimental observations. We also predict a stable high-voltage ordered compound LiMnNiO4, with a very high delithiation voltage of 4.76 V. For the composite (Mn-rich+Ni -rich) cathode materials, the voltage profiles show combinations of plateaus from each component compound. The computational strategy of combining quaternary phase diagrams with voltage calculations provides a pathway to understand and design concentration gradient materials.

  16. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4.

  17. Structural evolution and the capacity fade mechanism upon long-term cycling in Li-rich cathode material.

    PubMed

    Song, Bohang; Liu, Zongwen; Lai, Man On; Lu, Li

    2012-10-01

    High capacity Li-rich layered cathode Li(Li(0.2)Mn(0.54)Ni(0.13)Co(0.13))O(2) and doped one are investigated to understand mechanisms of capacity fade as well as voltage decrease upon long-term cycling. Detailed electrochemical analysis reveals a phase-separation-like behavior with increase in the cycle number, which is responsible for gradual reduction in discharge voltage. X-ray photoelectron spectroscopy (XPS), transmission electron microscope coupled with energy dispersive X-ray spectroscopy (TEM-EDS) and inductively coupled plasma emission spectrometry (ICP) analysis results show increase in valence of transition metals on the surface of powder at a fully discharged state in addition to surface dissolution of Ni, leading to rapid capacity loss. High resolution transmission electron microscopy (HR-TEM) shows a phase transformation from original layered structure into spinel-like nano-domains in local structure. Though such an unexpected structural change is unfavorable because of lower output voltage, it is observed to be beneficial for high-rate performance.

  18. Effect of titanium addition as nickel oxide formation inhibitor in nickel-rich cathode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Nurpeissova, Arailym; Choi, Moon Ho; Kim, Jik-Soo; Myung, Seung-Taek; Kim, Sung-Soo; Sun, Yang-Kook

    2015-12-01

    Among high capacity cathodes, LiNi0.8Co0.15Al0.05O2 has a high capacity and stable electrochemical performance, although it suffers from degradation upon cycling and aging as a result of the formation of inactive NiO on the surface edges. In this study, the role of Ti, which partially replaces Ni in the transition metal layer that is in particular intended to surface region not in bulk of LiNi0.8Co0.15Al0.05O2, is investigated on the electrochemical performance and interfacial phenomena using transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and X-ray diffraction analyses before and after electrochemical cycling. As a result, formation of NiO inactive phase is inhibited for the Ti-doped LiNi0.8Co0.15Al0.05O2, so that the electrode could deliver higher capacity upon cycling test. Further electrochemical impedance analysis is performed to understand the interfacial behavior of Ti-doped LiNi0.8Co0.15Al0.05O2 (LiNi0.80Co0.15Al0.02Ti0.03O2).

  19. Synthesis and electrochemical performance of lithium vanadium phosphate and lithium vanadium oxide composite cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Y.; Bai, W. Q.; Zhang, Y. D.; Niu, X. Q.; Wang, D. H.; Wang, X. L.; Gu, C. D.; Tu, J. P.

    2015-05-01

    A novel 2Li3V2(PO4)3·LiV3O8 composite with short rod and thin plate shapes is synthesized through sol-gel method followed by hydrothermal and solid-state reaction. LiV3O8 is used as an additive to improve the capacity of Li3V2(PO4)3. In the composite cathode, active impurity phase Li0.3V2O5 is also present, which has little impact on the whole electrochemical properties. The 2Li3V2(PO4)3·LiV3O8 composite delivers a high initial capacity of 162.8 mAh g-1 at a current density of 100 mA g-1 in the voltage range of 2.0-4.3 V. Furthermore, the composite with high crystallinity also shows high electrochemical reversibility and good rate capability. The diffusion coefficient of Li ions in the composite is in the range of 10-11-10-9 cm2 s-1 obtained from galvanostatic intermittent titration technique.

  20. Synthesis of Li2FeP2O7/Carbon nanocomposite as cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Nagano, Hiroaki; Taniguchi, Izumi

    2015-12-01

    A Li2FeP2O7/Carbon (C) nanocomposite was successfully synthesized via a combination of spray pyrolysis and wet ball milling followed by annealing from a precursor solution; in which LiNO3, H3PO4 and Fe(NO3)3·9H2O were stoichiometrically dissolved into distilled water. Ascorbic acid was added to the precursor solution as a reduction agent. The peaks of the Li2FeP2O7/C nanocomposite obtained by X-ray diffraction analysis were indexed to the monoclinic structure with the space group P21/c. The Li2FeP2O7/C nanocomposite cathode delivered a first discharge capacity of 100 mAh g-1 at 0.05 C, which corresponded to 91% of its theoretical capacity. After various higher discharge rates from 0.05 to 2 C in the cycle performance test, a discharge capacity of 93 mAh g-1 was achieved at 0.05 C, which showed an excellent capacity retention (93%) after 29 cycles.

  1. High contrast cathode ray tube

    NASA Technical Reports Server (NTRS)

    Lisovicz, E. J.; Catlaw, T. G. (Inventor)

    1971-01-01

    A layer of material is described, which contains fine grains of phosphor material stimulated by electrons to produce visible radiation. The layer, which also contains fine grains of cobalt oxide, is deposited on the glass screen of a cathode ray tube to provide high contrast, by absorbing most of the visible radiation which is directed to the layer through the screen, while not materially affecting the visible light which the phosphor material produces in response to the electron stimulation.

  2. Improving the rate capability of high voltage lithium-ion battery cathode material LiNi0.5Mn1.5O4 by ruthenium doping

    NASA Astrophysics Data System (ADS)

    Kiziltas-Yavuz, Nilüfer; Bhaskar, Aiswarya; Dixon, Ditty; Yavuz, Murat; Nikolowski, Kristian; Lu, Li; Eichel, Rüdiger-A.; Ehrenberg, Helmut

    2014-12-01

    The citric acid-assisted sol-gel method was used to produce the high-voltage cathodes LiNi0.5Mn1.5O4 and LiNi0.4Ru0.05Mn1.5O4 at 800 °C and 1000 °C final calcination temperatures. High resolution powder diffraction using synchrotron radiation, inductively coupled plasma - optical emission spectroscopy and scanning electron microscopy analyses were carried out to characterize the structure, chemical composition and morphology. X-ray absorption spectroscopy studies were conducted to confirm Ru doping inside the spinel as well as to compare the oxidation states of transition metals. The formation of an impurity LixNi1-xO in LiNi0.5Mn1.5O4 powders annealed at high temperatures (T ≥ 800 °C) can be suppressed by partial substitution of Ni2+ by Ru4+ ion. The LiNi0.4Ru0.05Mn1.5O4 powder synthesized at 1000 °C shows the highest performance regarding the rate capability and cycling stability. It has an initial capacity of ∼139 mAh g-1 and capacity retention of 84% after 300 cycles at C/2 charging-discharging rate between 3.5 and 5.0 V. The achievable discharge capacity at 20 C for a charging rate of C/2 is ∼136 mAh g-1 (∼98% of the capacity delivered at C/2). Since the electrode preparation plays a crucial role on parameters like the rate capability, the influence of the mass loading of active materials in the cathode mixture is discussed.

  3. Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization

    PubMed Central

    2015-01-01

    The oxygen exchange activity of mixed conducting oxide surfaces has been widely investigated, but a detailed understanding of the corresponding reaction mechanisms and the rate-limiting steps is largely still missing. Combined in situ investigation of electrochemically polarized model electrode surfaces under realistic temperature and pressure conditions by near-ambient pressure (NAP) XPS and impedance spectroscopy enables very surface-sensitive chemical analysis and may detect species that are involved in the rate-limiting step. In the present study, acceptor-doped perovskite-type La0.6Sr0.4CoO3-δ (LSC), La0.6Sr0.4FeO3-δ (LSF), and SrTi0.7Fe0.3O3-δ (STF) thin film model electrodes were investigated under well-defined electrochemical polarization as cathodes in oxidizing (O2) and as anodes in reducing (H2/H2O) atmospheres. In oxidizing atmosphere all materials exhibit additional surface species of strontium and oxygen. The polaron-type electronic conduction mechanism of LSF and STF and the metal-like mechanism of LSC are reflected by distinct differences in the valence band spectra. Switching between oxidizing and reducing atmosphere as well as electrochemical polarization cause reversible shifts in the measured binding energy. This can be correlated to a Fermi level shift due to variations in the chemical potential of oxygen. Changes of oxidation states were detected on Fe, which appears as FeIII in oxidizing atmosphere and as mixed FeII/III in H2/H2O. Cathodic polarization in reducing atmosphere leads to the reversible formation of a catalytically active Fe0 phase. PMID:26877827

  4. Gram-scale synthesis of catalytic Co9S8 nanocrystal ink as a cathode material for spray-deposited, large-area dye-sensitized solar cells.

    PubMed

    Chang, Shu-Hao; Lu, Ming-De; Tung, Yung-Liang; Tuan, Hsing-Yu

    2013-10-22

    We report the development of Co9S8 nanocrystals as a cost-effective cathode material that can be readily combined with spraying techniques to fabricate large-area dye-sensitized solar cell (DSSC) devices and can be further connected with series or parallel cell architectures to obtain a relatively high output voltage or current. A gram-scale synthesis of Co9S8 nanocrystal is carried out via a noninjection reaction by mixing anhydrous CoCl2 with trioctylphosphine (TOP), dodecanethiol and oleylamine (OLA) at 250 °C. The Co9S8 nanocrystals possess excellent catalytic ability with respect to I(-)/I3(-) redox reactions. The Co9S8 nanocrystals are prepared as nanoinks to fabricate uniform, crack-free Co9S8 thin films on different substrates by using a spray deposition technique. These Co9S8 films are used as counter electrodes assembled with dye-adsorbed TiO2 photoanodes to fabricate DSSC devices having a working area of 2 cm(2) and an average power conversion efficiency (PCE) of 7.02 ± 0.18% under AM 1.5 solar illumination, which is comparable with the PCE of 7.2 ± 0.12% obtained using a Pt cathode. Furthermore, six 2 cm(2)-sized DSSC devices connected in series output an open-circuit voltage of 4.2 V that can power a wide range of electronic devices such as LED arrays and can charge commercial lithium ion batteries. PMID:23992127

  5. Porous nitrogen-doped carbon derived from silk fibroin protein encapsulating sulfur as a superior cathode material for high-performance lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Jiawei; Cai, Yurong; Zhong, Qiwei; Lai, Dongzhi; Yao, Juming

    2015-10-01

    The features of a carbon substrate are crucial for the electrochemical performance of lithium-sulfur (Li-S) batteries. Nitrogen doping of carbon materials is assumed to play an important role in sulfur immobilisation. In this study, natural silk fibroin protein is used as a precursor of nitrogen-rich carbon to fabricate a novel, porous, nitrogen-doped carbon material through facile carbonisation and activation. Porous carbon, with a reversible capacity of 815 mA h g-1 at 0.2 C after 60 cycles, serves as the cathode material in Li-S batteries. Porous carbon retains a reversible capacity of 567 mA h g-1, which corresponds to a capacity retention of 98% at 1 C after 200 cycles. The promising electrochemical performance of porous carbon is attributed to its mesoporous structure, high specific surface area and nitrogen doping into the carbon skeleton. This study provides a general strategy to synthesise nitrogen-doped carbons with a high specific surface area, which is crucial to improve the energy density and electrochemical performance of Li-S batteries.

  6. Preparation and electrical properties of Ca-doped La(2)NiO(4+δ) cathode materials for IT-SOFC.

    PubMed

    Shen, Yongna; Zhao, Hailei; Liu, Xiaotong; Xu, Nansheng

    2010-12-01

    Ca-doped La(2)NiO(4+δ) is synthesized via the nitrate-citrate route. The effects of Ca substitution for La on the sinterability, lattice structure and electrical properties of La(2)NiO(4+δ) are investigated. Ca-doping is unfavorable for the densification process of La(2-x)Ca(x)NiO(4+δ) materials. The introduction of Ca leads to the elongation of the La-O(2) bond length, which provides more space for the migration of oxygen ion in La(2)O(2) rock salt layers. The substitution of Ca increases remarkably the electronic conductivity of La(2-x)Ca(x)NiO(4+δ). With increasing Ca-doping level, both the excess oxygen concentration and the activation energy of oxygen ion migration decrease, resulting in an optimization where a highest ionic conductivity is presented. Ca-doping is charge compensated by the oxidation of Ni(2+) to Ni(3+) and the desorption of excess oxygen. The substitution of Ca enhances the structural stability of La(2)NiO(4+δ) material at high temperatures and renders the material a good thermal cycleability. La(1.7)Ca(0.3)NiO(4+δ) exhibits an excellent chemical compatibility with CGO electrolyte. La(2-x)Ca(x)NiO(4+δ) is a promising cathode alternative for solid oxide fuel cells. PMID:20967398

  7. Porous nitrogen-doped carbon derived from silk fibroin protein encapsulating sulfur as a superior cathode material for high-performance lithium-sulfur batteries.

    PubMed

    Zhang, Jiawei; Cai, Yurong; Zhong, Qiwei; Lai, Dongzhi; Yao, Juming

    2015-11-14

    The features of a carbon substrate are crucial for the electrochemical performance of lithium-sulfur (Li-S) batteries. Nitrogen doping of carbon materials is assumed to play an important role in sulfur immobilisation. In this study, natural silk fibroin protein is used as a precursor of nitrogen-rich carbon to fabricate a novel, porous, nitrogen-doped carbon material through facile carbonisation and activation. Porous carbon, with a reversible capacity of 815 mA h g(-1) at 0.2 C after 60 cycles, serves as the cathode material in Li-S batteries. Porous carbon retains a reversible capacity of 567 mA h g(-1), which corresponds to a capacity retention of 98% at 1 C after 200 cycles. The promising electrochemical performance of porous carbon is attributed to its mesoporous structure, high specific surface area and nitrogen doping into the carbon skeleton. This study provides a general strategy to synthesise nitrogen-doped carbons with a high specific surface area, which is crucial to improve the energy density and electrochemical performance of Li-S batteries.

  8. Surface Morphology and Surface Stability against Oxygen Loss of the Lithium-Excess Li2MnO3 Cathode Material as a Function of Lithium Concentration.

    PubMed

    Shin, Yongwoo; Persson, Kristin A

    2016-09-28

    There is a growing appreciation for the role of surface reactivity and subsequent reconstruction affecting the performance of high-voltage, high-capacity Li-ion cathode materials. In particular, the promising Li-excess materials are known to exhibit significant vulnerability toward oxygen release, which can cause surface densification and impede Li intercalation. Here we focus on the end member, Li2MnO3, as a Li-excess, Mn-rich representative of this class of materials and systematically elucidate all possible stoichiometric low Miller index surfaces with various cation ordering on each surface. We apply surface cation reconstruction rules that depend on the local environment, including target Mn-Li site exchanges, and optimize the resulting surface Li configurations using metadynamics. The equilibrium Wulff shape shows dominant (001), (010) surface facets, and almost all facets exhibit favorable Mn reconstruction. Most importantly, we find that while all equilibrium LixMnO3 surfaces become unstable toward oxygen release for x < 1.7, some facets are consistently more resistant than others which may provide a design metric for more stable particle morphologies and enhanced surface oxygen retention.

  9. Effect of Iron-based Impurities on the performance of nanostructured C-LiFePO4 cathode materials for Li ion Batteries

    NASA Astrophysics Data System (ADS)

    Vaishnava, P.; Dixit, A.; Bazzi, K.; Sahana, M. B.; Sudakar, C.; Nazri, M.; Naik, V.; Garg, V. K.; Oliveira, A. C.; Nazri, G. A.; Naik, R.

    2012-02-01

    We report synthesis of pure and C-LiFePO4 nanoparticles in 20-30 nm size by sol-gel method. Three samples of C-LiFePO4 were prepared by mixing 0.25M, 0.50M, and 1M lauric acid in the precursor solutions for carbon coating the particles. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), IR spectroscopy, SQUID magnetometery, Raman spectroscopy, and Fe^57 M"ossbauer spectroscopy. All the samples were thoroughly investigated for their electrochemical properties. The XRD measurements showed all the samples are single phase materials with no impurity phase. However, we identified at least three residual non crystalline impurity phases simultaneously using Fe^57 M"ossbauer spectroscopy, XPS, and the magnetic measurements. The elemental chemical states for Fe 2p, P 2p, and O 1s are analyzed using XPS for LiFePO4 and compared with those of C-LiFePO4 materials. SQUID magnetometery measurements suggest an antiferromagnetic transition ˜50 K in both pure LiFePO4 and C-LiFePO4 samples. The role of various phases, such as FeP, Fe2P, α-Fe and Fe2O3 identified and analyzed by Fe^57 M"ossbauer spectroscopy and XPS, will be discussed in relationship to the electrochemical properties of the cathode materials.

  10. A High-Voltage and High-Capacity Li1+x Ni0.5 Mn1.5 O4 Cathode Material: From Synthesis to Full Lithium-Ion Cells.

    PubMed

    Mancini, Marilena; Axmann, Peter; Gabrielli, Giulio; Kinyanjui, Michael; Kaiser, Ute; Wohlfahrt-Mehrens, Margret

    2016-07-21

    We report Co-free, Li-rich Li1+x Ni0.5 Mn1.5 O4 (0cathode materials for Li-ion cells. Their tailored morphology allows high density and facile processability for electrode development. In the potential range 2.4-4.9 V, the cathode material of composition Li1.5 Ni0.5 Mn1.5 O4 shows excellent performance in terms of capacity and cycling stability in half-cells. In addition, for the first time, we demonstrate the application of the high-voltage and high-capacity cathode in full Li-ion cells with graphite anodes with very high cycling stability. The electrochemical performance and low cost of the cathode material, together with the feasibility of a chemical method to obtain Li-rich Li1+x Ni0.5 Mn1.5 O4 (0

  11. A High-Voltage and High-Capacity Li1+x Ni0.5 Mn1.5 O4 Cathode Material: From Synthesis to Full Lithium-Ion Cells.

    PubMed

    Mancini, Marilena; Axmann, Peter; Gabrielli, Giulio; Kinyanjui, Michael; Kaiser, Ute; Wohlfahrt-Mehrens, Margret

    2016-07-21

    We report Co-free, Li-rich Li1+x Ni0.5 Mn1.5 O4 (0cathode materials for Li-ion cells. Their tailored morphology allows high density and facile processability for electrode development. In the potential range 2.4-4.9 V, the cathode material of composition Li1.5 Ni0.5 Mn1.5 O4 shows excellent performance in terms of capacity and cycling stability in half-cells. In addition, for the first time, we demonstrate the application of the high-voltage and high-capacity cathode in full Li-ion cells with graphite anodes with very high cycling stability. The electrochemical performance and low cost of the cathode material, together with the feasibility of a chemical method to obtain Li-rich Li1+x Ni0.5 Mn1.5 O4 (0

  12. Hollow cathode apparatus

    NASA Technical Reports Server (NTRS)

    Aston, G. (Inventor)

    1984-01-01

    A hollow cathode apparatus is described, which can be rapidly and reliably started. An ignitor positioned upstream from the hollow cathode, generates a puff of plasma that flows with the primary gas to be ionized through the cathode. The plasma puff creates a high voltage breakdown between the downstream end of the cathode and a keeper electrode, to heat the cathode to an electron-emitting temperature.

  13. Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.

    PubMed

    Yang, Shiliu; Hu, Mingjun; Xi, Liujiang; Ma, Ruguang; Dong, Yucheng; Chung, C Y

    2013-09-25

    A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

  14. Hierarchical Carbon with High Nitrogen Doping Level: A Versatile Anode and Cathode Host Material for Long-Life Lithium-Ion and Lithium-Sulfur Batteries.

    PubMed

    Reitz, Christian; Breitung, Ben; Schneider, Artur; Wang, Di; von der Lehr, Martin; Leichtweiss, Thomas; Janek, Jürgen; Hahn, Horst; Brezesinski, Torsten

    2016-04-27

    Nitrogen-rich carbon with both a turbostratic microstructure and meso/macroporosity was prepared by hard templating through pyrolysis of a tricyanomethanide-based ionic liquid in the voids of a silica monolith template. This multifunctional carbon not only is a promising anode candidate for long-life lithium-ion batteries but also shows favorable properties as anode and cathode host material owing to a high nitrogen content (>8% after carbonization at 900 °C). To demonstrate the latter, the hierarchical carbon was melt-infiltrated with sulfur as well as coated by atomic layer deposition (ALD) of anatase TiO2, both of which led to high-quality nanocomposites. TiO2 ALD increased the specific capacity of the carbon while maintaining high Coulombic efficiency and cycle life: the composite exhibited stable performance in lithium half-cells, with excellent recovery of low rate capacities after thousands of cycles at 5C. Lithium-sulfur batteries using the sulfur/carbon composite also showed good cyclability, with reversible capacities of ∼700 mA·h·g(-1) at C/5 and without obvious decay over several hundred cycles. The present results demonstrate that nitrogen-rich carbon with an interconnected multimodal pore structure is very versatile and can be used as both active and inactive electrode material in high-performance lithium-based batteries. PMID:26867115

  15. Synthesis of spinel LiNi0.5Mn1.5O4 with secondary plate morphology as cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Risthaus, Tim; Wang, Jun; Friesen, Alex; Wilken, Andrea; Berghus, Debbie; Winter, Martin; Li, Jie

    2015-10-01

    Spinel LiNi0.5Mn1.5O4 material has been synthesized by a spray drying process and subsequent solid state reaction. Polyvinylpyrrolidone (PVP) is given as additive to the spray drying precursor solution and its effects on structural and electrochemical properties are evaluated. By using PVP in the synthesis process, the obtained sample displays a secondary plate morphology which is consisting of densely arranged primary octahedrally shaped particles. The new cathode material has a lesser degree of impurity phases, a higher discharge capacity, a superior rate capability, and a slightly better cycling performance than the sample synthesized without PVP. In more detail, by the use of PVP the ratio of Mn3+ to Mn4+ in the final product decreases from 20.8 to 9.2%. The initial discharge capacity at 0.1 C exhibits an increase of about 14%. The normalized capacity at 20 C is 84.1% instead of 67.0%. A slightly improved cycling performance with the capacity retention increase from 93.8 to 97.9% could be observed as well.

  16. Utilizing environmental friendly iron as a substitution element in spinel structured cathode materials for safer high energy lithium-ion batteries

    SciTech Connect

    Hu, Enyuan; Bak, Seong -Min; Liu, Yijin; Liu, Jue; Yu, Xiqian; Zhou, Yong -Ning; Zhou, Jigang; Khalifah, Peter; Ariyoshi, Kingo; Nam, Kyung -Wan; Yang, Xiao -Qing

    2015-12-03

    Suppressing oxygen release from lithium ion battery cathodes during heating is a critical issue for the improvement of the battery safety characteristics because oxygen can exothermically react with the flammable electrolyte and cause thermal runaway. Previous studies have shown that oxygen release can be reduced by the migration of transition metal cations from octahedral sites to tetrahedral sites during heating. Such site-preferred migration is determined by the electronic structure of cations. In addition, taking advantage of the unique electronic structure of the environmental friendly Fe, this is selected as substitution element in a high energy density material LiNi0.5Mn1.5O4 to improve the thermal stability. The optimized LiNi0.33Mn1.33Fe0.33O4 material shows significantly improved thermal stability compared with the unsubstituted one, demonstrated by no observed oxygen release at temperatures as high as 500°C. Due to the electrochemical contribution of Fe, the high energy density feature of LiNi0.5Mn1.5O4 is well preserved.

  17. Utilizing environmental friendly iron as a substitution element in spinel structured cathode materials for safer high energy lithium-ion batteries

    DOE PAGES

    Hu, Enyuan; Bak, Seong -Min; Liu, Yijin; Liu, Jue; Yu, Xiqian; Zhou, Yong -Ning; Zhou, Jigang; Khalifah, Peter; Ariyoshi, Kingo; Nam, Kyung -Wan; et al

    2015-12-03

    Suppressing oxygen release from lithium ion battery cathodes during heating is a critical issue for the improvement of the battery safety characteristics because oxygen can exothermically react with the flammable electrolyte and cause thermal runaway. Previous studies have shown that oxygen release can be reduced by the migration of transition metal cations from octahedral sites to tetrahedral sites during heating. Such site-preferred migration is determined by the electronic structure of cations. In addition, taking advantage of the unique electronic structure of the environmental friendly Fe, this is selected as substitution element in a high energy density material LiNi0.5Mn1.5O4 to improvemore » the thermal stability. The optimized LiNi0.33Mn1.33Fe0.33O4 material shows significantly improved thermal stability compared with the unsubstituted one, demonstrated by no observed oxygen release at temperatures as high as 500°C. Due to the electrochemical contribution of Fe, the high energy density feature of LiNi0.5Mn1.5O4 is well preserved.« less

  18. AlF3-coated LiMn2O4 as cathode material for aqueous rechargeable lithium battery with improved cycling stability

    NASA Astrophysics Data System (ADS)

    Tron, Artur; Park, Yeong Don; Mun, Junyoung

    2016-09-01

    In this study, we introduce AlF3-coated LiMn2O4 cathodes, which are cost-effective and environmentally benign, for use in the aqueous rechargeable lithium-ion battery. The homogeneous AlF3 coating on the LiMn2O4 powder is synthesized by a simple chemical deposition method. The thickness of the coating is controlled by varying the quantity of AlF3 used, in order to optimize the balance between polarization and surface stabilization. The optimized LiMn2O4, having 2 wt% coating of AlF3, exhibits a long cycle life having a capacity retention of 90% after 100 cycles, and a highly improved rate capability, when compared with the pristine LiMn2O4 material, in 1 M Li2SO4 aqueous electrolyte solution. The systematic surface analyses, comprising scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical analyses, indicate that the AlF3 coating on the LiMn2O4 surface successfully reduces the surface deterioration of LiMn2O4 caused by side reactions between the electrolyte solution and the active material.

  19. Study of the surface modification of LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Hashem, A. M. A.; Abdel-Ghany, A. E.; Eid, A. E.; Trottier, J.; Zaghib, K.; Mauger, A.; Julien, C. M.

    2011-10-01

    The surface of LiNi1/3Co1/3Mn1/3O2 (LNMCO) particles has been studied for material synthesized at 900 °C by a two-step process from a mixture of LiOH·H2O and metal oxalate [(Ni1/3Co1/3Mn1/3)C2O4] obtained by co-precipitation. Samples have been characterized by X-ray diffraction (XRD), high-resolution transmission electron microscope (HRTEM), Raman scattering (RS) spectroscopy, and magnetic measurements. We have investigated the effect of the heat treatment of particles at 600 °C with organic substances such as sucrose and starch. HRTEM images and RS spectra indicate that the surface of particles has been modified. The annealing does not lead to any carbon coating but it leads to the crystallization of the thin disordered layer on the surface of LiNi1/3Co1/3Mn1/3O2. The beneficial effect has been tested on the electrochemical properties of the LiNi1/3Co1/3Mn1/3O2 cathode materials. The capacity at 10C-rate is enhanced by 20% for post-treated LNMCO particles at 600 °C for half-an-hour.

  20. Density functional theory study on oxygen adsorption in LaSrCoO 4: An extended cathode material for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, Jun; Chen, Gang; Wu, Kai; Cheng, Yonghong; Peng, Bo; Guo, Jiaojiao; Jiang, Yizhe

    2012-01-01

    Solid oxide fuel cell (SOFC) is one of the most promising technologies for a clean and secure source of energy in future due to its high energy efficiency and outstanding fuel flexibility. The search for new materials operating at low-temperature in order to make SOFCs economically competitive is a great challenge facing us today. In this report, atomistic computer simulation based on density functional theory (DFT) has been used to predict the formation of oxygen vacancy and the strong oxygen adsorption kinetics mechanisms in LaSrCoO4. The optimal adsorption configurations as well as the adsorption energies for oxygen molecule adsorption on various sites of LaSrCoO4 (0 1 0) surface were derived. Furthermore, a strong hybridization between Co and O and shorter Co-O bond length for molecular adsorption were obtained by analysis of density of states. The calculated results imply that LaSrCoO4 could serve as possible cathode material due to its low formation and migration energies of oxygen vacancies.

  1. Controllable synthesis of spinel lithium nickel manganese oxide cathode material with enhanced electrochemical performances through a modified oxalate co-precipitation method

    NASA Astrophysics Data System (ADS)

    Liu, Hongmei; Zhu, Guobin; Zhang, Li; Qu, Qunting; Shen, Ming; Zheng, Honghe

    2015-01-01

    A spinel lithium nickel manganese oxide (LiNi0.5Mn1.5O4) cathode material is synthesized with a modified oxalate co-precipitation method by controlling pH value of the precursor solution and introducing excessive Li source in the precursor. All the samples synthesized through this method are of Fd3m phase with a small amount of P4332 phase. It is found that pH value of the precursor solution considerably affects the morphology, stoichiometry and crystallographic structure of the target material, thereby resulting in different amounts of Mn3+ (i.e., different degree of disorder). 5% excessive Li source in the precursor may compensate for the lithium loss during the high-temperature sintering process and eliminate the LixNi1-xO impurity phase. Under the optimized synthesis conditions, the obtained high-purity LiNi0.5Mn1.5O4 spinel exhibits enhanced electrochemical performances. A reversible capacity of ca. 140 mAh g-1 can be delivered at 0.1C and the electrode retains 106 mAh g-1 at 10C rate. When cycled at 0.2C, a capacity retention of more than 98% is obtained in the initial 50 electrochemical cycles.

  2. A portable x-ray source with a nanostructured Pt-coated silicon field emission cathode for absorption imaging of low-Z materials

    NASA Astrophysics Data System (ADS)

    Basu, Anirban; Swanwick, Michael E.; Fomani, Arash A.; Velásquez-García, Luis Fernando

    2015-06-01

    We report the design, fabrication, and characterization of a portable x-ray generator for imaging of low-atomic number materials such as biological soft tissue. The system uses a self-aligned, gated, Pt-coated silicon field emitter cathode with two arrays of 62 500 nano-sharp tips arranged in a square grid with 10 μm emitter pitch, and a natural convection-cooled reflection anode composed of a Cu bar coated with a thin Mo film. Characterization of the field emitter array demonstrated continuous emission of 1 mA electron current (16 mA cm  -  2) with  >95% current transmission at a 150 V gate-emitter bias voltage for over 20 h with no degradation. The emission of the x-ray source was characterized across a range of anode bias voltages to maximize the fraction of photons from the characteristic K-shell peaks of the Mo film to produce a quasi-monochromatic photon beam, which enables capturing high-contrast images of low-atomic number materials. The x-ray source operating at the optimum anode bias voltage, i.e. 35 kV, was used to image ex vivo and nonorganic samples in x-ray fluoroscopic mode while varying the tube current; the images resolve feature sizes as small as ~160 µm.

  3. Arc initiation in cathodic arc plasma sources

    DOEpatents

    Anders, Andre

    2002-01-01

    A "triggerless" arc initiation method and apparatus is based on simply switching the arc supply voltage to the electrodes (anode and cathode). Neither a mechanical trigger electrode nor a high voltage flashover from a trigger electrode is required. A conducting path between the anode and cathode is provided, which allows a hot spot to form at a location where the path connects to the cathode. While the conductive path is eroded by the cathode spot action, plasma deposition ensures the ongoing repair of the conducting path. Arc initiation is achieved by simply applying the relatively low voltage of the arc power supply, e.g. 500 V-1 kV, with the insulator between the anode and cathode coated with a conducting layer and the current at the layer-cathode interface concentrated at one or a few contact points. The local power density at these contact points is sufficient for plasma production and thus arc initiation. A conductive surface layer, such as graphite or the material being deposited, is formed on the surface of the insulator which separates the cathode from the anode. The mechanism of plasma production (and arc initiation) is based on explosive destruction of the layer-cathode interface caused by joule heating. The current flow between the thin insulator coating and cathode occurs at only a few contact points so the current density is high.

  4. Emission properties of explosive field emission cathodes

    SciTech Connect

    Roy, Amitava; Patel, Ankur; Menon, Rakhee; Sharma, Archana; Chakravarthy, D. P.; Patil, D. S.

    2011-10-15

    The research results of the explosive field emission cathode plasma expansion velocity and the initial emission area in the planar diode configuration with cathodes made of graphite, stainless steel, polymer velvet, carbon coated, and carbon fiber (needle type) cathodes are presented. The experiments have been performed at the electron accelerator LIA-200 (200 kV, 100 ns, and 4 kA). The diode voltage has been varied from 28-225 kV, whereas the current density has been varied from 86-928 A/cm{sup 2} with 100 ns pulse duration. The experimentally obtained electron beam diode perveance has been compared with the 1 dimensional Child-Langmuir- law. It was found that initially only a part of the cathode take part in the emission process. The plasma expands at 1.7-5.2 cm/{mu}s for 4 mm anode-cathode gap for various cathode materials. It was found that the plasma expansion velocity increases with the decrease in the cathode diameter. At the beginning of the accelerating pulse, the entire cathode area participates in the electron emission process only for the multiple needle type carbon fiber cathode.

  5. Highly efficient and robust cathode materials for low-temperature solid oxide fuel cells: PrBa0.5Sr0.5Co(2-x)Fe(x)O(5+δ).

    PubMed

    Choi, Sihyuk; Yoo, Seonyoung; Kim, Jiyoun; Park, Seonhye; Jun, Areum; Sengodan, Sivaprakash; Kim, Junyoung; Shin, Jeeyoung; Jeong, Hu Young; Choi, YongMan; Kim, Guntae; Liu, Meilin

    2013-01-01

    Solid oxide fuel cells (SOFC) are the cleanest, most efficient, and cost-effective option for direct conversion to electricity of a wide variety of fuels. While significant progress has been made in anode materials with enhanced tolerance to coking and contaminant poisoning, cathodic polarization still contributes considerably to energy loss, more so at lower operating temperatures. Here we report a synergistic effect of co-doping in a cation-ordered double-perovskite material, PrBa0.5Sr0.5Co(2-x)Fe(x)O(5+δ), which has created pore channels that dramatically enhance oxygen ion diffusion and surface oxygen exchange while maintaining excellent compatibility and stability under operating conditions. Test cells based on these cathode materials demonstrate peak power densities ~2.2 W cm(-2) at 600°C, representing an important step toward commercially viable SOFC technologies.

  6. Highly efficient and robust cathode materials for low-temperature solid oxide fuel cells: PrBa0.5Sr0.5Co2-xFexO5+δ

    NASA Astrophysics Data System (ADS)

    Choi, Sihyuk; Yoo, Seonyoung; Kim, Jiyoun; Park, Seonhye; Jun, Areum; Sengodan, Sivaprakash; Kim, Junyoung; Shin, Jeeyoung; Jeong, Hu Young; Choi, Yongman; Kim, Guntae; Liu, Meilin

    2013-08-01

    Solid oxide fuel cells (SOFC) are the cleanest, most efficient, and cost-effective option for direct conversion to electricity of a wide variety of fuels. While significant progress has been made in anode materials with enhanced tolerance to coking and contaminant poisoning, cathodic polarization still contributes considerably to energy loss, more so at lower operating temperatures. Here we report a synergistic effect of co-doping in a cation-ordered double-perovskite material, PrBa0.5Sr0.5Co2-xFexO5+δ, which has created pore channels that dramatically enhance oxygen ion diffusion and surface oxygen exchange while maintaining excellent compatibility and stability under operating conditions. Test cells based on these cathode materials demonstrate peak power densities ~2.2 W cm-2 at 600°C, representing an important step toward commercially viable SOFC technologies.

  7. Cathode for molten salt batteries

    DOEpatents

    Mamantov, Gleb; Marassi, Roberto

    1977-01-01

    A molten salt electrochemical system for battery applications comprises tetravalent sulfur as the active cathode material with a molten chloroaluminate solvent comprising a mixture of AlCl.sub.3 and MCl having a molar ratio of AlCl.sub.3 /MCl from greater than 50.0/50.0 to 80/20.

  8. Role of Ce and In doping in the performance of LiFePO4 cathode material for Li ion Batteries

    NASA Astrophysics Data System (ADS)

    Mandal, Balaji; Nazri, Mariam; Vaishnava, Prem P.; Naik, Vaman M.; Nazri, Gholam A.; Naik, Ratna

    2012-02-01

    Recently, the olivine LiFePO4 has attracted attention as a promising cathode material for Li ion batteries. However, its poor electronic conductivity is a major challenge for its industrial applications. Different approaches have been taken to address this problem. Here, we report a method of improving its conductivity by doping In and Ce ions at the Fe site. We prepared the samples by sol-gel method followed by annealing at 650 C in Ar (95%) +H2(5%) atmosphere for 5 hrs. XRD and Raman spectroscopy confirm that the olivine structure remains unchanged upon doping with In and Ce up to 5 wt%. XRD analysis shows the values of the lattice parameters increase with doping as the ionic radii of Ce and In ions are larger than that of the Fe^2+ ion. This observation also suggests that both Ce and In ions replace Fe ions and not the Li ions in the material. Upon doping, ionic conductivity was found to increase from 10-9 to 10-4 Ohm-1cm-1. Interestingly, Ce doped LiFePO4 showed a higher conductivity than In doped LiFePO4. SEM measurements show a bigger grain size of ˜300-500 nm in doped LiFePO4 which decreased to ˜50 nm when the materials were synthesized using 0.25M lauric acid as a precursor. The electrochemical characteristics of the doped LiFePO4 along with conductivity and Raman data will be presented.

  9. Recent Advances in Thermionic Cathodes

    SciTech Connect

    Ives, R. Lawrence; Miram, George; Collins, George; Falce, Louis R.

    2010-11-04

    The latest advances in thermionic cathodes, including scandate and controlled porosity reservoir cathodes, are reviewed. These new cathodes provide improved performance over conventional cathodes for many applications. Advantages and disadvantages are presented.

  10. Ultrathin Na1.1V3O7.9 nanobelts with superior performance as cathode materials for lithium-ion batteries.

    PubMed

    Liang, Shuquan; Zhou, Jiang; Fang, Guozhao; Liu, Jing; Tang, Yan; Li, Xilin; Pan, Anqiang

    2013-09-11

    The Na1.1V3O7.9 nanobelts have been synthesized by a facile and scalable hydrothermal reaction with subsequent calcinations. The morphologies and the crystallinity of the nanobelts are largely determined by the calcination temperatures. Ultrathin nanobelts with a thickness around 20 nm can be obtained, and the TEM reveals that the nanobelts are composed of many stacked thinner belts. When evaluated as a cathode material for lithium batteries, the Na1.1V3O7.9 nanobelts exhibit high specific capacity, good rate capability, and superior long-term cyclic stability. A high specific capacity of 204 mA h g(-1) can be delivered at the current density of 100 mA g(-1). It shows excellent capacity retention of 95% after 200 cycles at the current density of 1500 mA g(-1). As demonstrated by the ex situ XRD results, the Na1.1V3O7.9 nanobelts have very good structural stability upon cycling. The superior electrochemical performances can be attributed to the ultra-thin nanobelts and the good structural stability of the Na1.1V3O7.9 nanobelts.

  11. Li3V2(PO4)3@C core-shell nanocomposite as a superior cathode material for lithium-ion batteries.

    PubMed

    Duan, Wenchao; Hu, Zhe; Zhang, Kai; Cheng, Fangyi; Tao, Zhanliang; Chen, Jun

    2013-07-21

    Li3V2(PO4)3@C core-shell nanoparticles with typical sizes of 20-40 nm were synthesized using a hydrothermal-assisted sol-gel method. Ascorbic acid and PEG-400 were adopted as carbon sources and reductants. The uniform Li3V2(PO4)3@C nanocomposite obtained was composed of a Li3V2(PO4)3 core with high-phase purity and a graphitized carbon shell, which was characterized using XRD, SEM, TEM, and Raman analysis. The nanocomposite exhibited a remarkably high rate capability and long cyclability, delivering a discharge capacity of 138 mA h g(-1) at 5 C within a voltage range of 3-4.8 V and the capacity retention was 86% after 1000 cycles. The superior electrochemical performance of Li3V2(PO4)3@C indicates that it has potential for application as a cathode material in advanced rechargeable lithium-ion batteries.

  12. Ascorbic Acid-Assisted Synthesis of Mesoporous Sodium Vanadium Phosphate Nanoparticles with Highly sp(2) -Coordinated Carbon Coatings as Efficient Cathode Materials for Rechargeable Sodium-Ion Batteries.

    PubMed

    Hung, Tai-Feng; Cheng, Wei-Jen; Chang, Wen-Sheng; Yang, Chang-Chung; Shen, Chin-Chang; Kuo, Yu-Lin

    2016-07-18

    Herein, mesoporous sodium vanadium phosphate nanoparticles with highly sp(2) -coordinated carbon coatings (meso-Na3 V2 (PO4 )3 /C) were successfully synthesized as efficient cathode material for rechargeable sodium-ion batteries by using ascorbic acid as both the reductant and carbon source, followed by calcination at 750 °C in an argon atmosphere. Their crystalline structure, morphology, surface area, chemical composition, carbon nature and amount were systematically explored. Following electrochemical measurements, the resultant meso-Na3 V2 (PO4 )3 /C not only delivered good reversible capacity (98 mAh g(-1) at 0.1 A g(-1) ) and superior rate capability (63 mAh g(-1) at 1 A g(-1) ) but also exhibited comparable cycling performance (capacity retention: ≈74 % at 450 cycles at 0.4 A g(-1) ). Moreover, the symmetrical sodium-ion full cell with excellent reversibility and cycling stability was also achieved (capacity retention: 92.2 % at 0.1 A g(-1) with 99.5 % coulombic efficiency after 100 cycles). These attributes are ascribed to the distinctive mesostructure for facile sodium-ion insertion/extraction and their continuous sp(2) -coordinated carbon coatings, which facilitate electronic conduction.

  13. Detailed investigation of Na2.24FePO4CO3 as a cathode material for Na-ion batteries

    PubMed Central

    Huang, Weifeng; Zhou, Jing; Li, Biao; Ma, Jin; Tao, Shi; Xia, Dingguo; Chu, Wangsheng; Wu, Ziyu

    2014-01-01

    Na-ion batteries are gaining an increased recognition as the next generation low cost energy storage devices. Here, we present a characterization of Na3FePO4CO3 nanoplates as a novel cathode material for sodium ion batteries. First-principles calculations reveal that there are two paths for Na ion migration along b and c axis. In-situ and ex-situ Fe K-edge X-ray absorption near edge structure (XANES) point out that in Na3FePO4CO3 both Fe2+/Fe3+ and Fe3+/Fe4+ redox couples are electrochemically active, suggesting also the existence of a two-electron intercalation reaction. Ex-situ X-ray powder diffraction data demonstrates that the crystalline structure of Na3FePO4CO3 remains stable during the charging/discharging process within the range 2.0–4.55 V. PMID:24595232

  14. High-rate performance electrospun Na0.44MnO2 nanofibers as cathode material for sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Fu, Bi; Zhou, Xuan; Wang, Yaping

    2016-04-01

    Sodium-ion batteries (SIBs) are considered as one of the most promising candidates to replace lithium-ion batteries (LIBs), because of their similar electrochemical properties, and geographical limitations of lithium. However, searching for the appropriate cathode materials for SIBs that can accommodate structure change during the insertion and extraction of sodium ions is facing great challenges due to the relatively larger size of sodium ion. Na0.44MnO2 has recently attracted significant attention because its crystal structure exhibits two types of large channels formed by MnO6 octahedra and MnO5 square pyramids, which facilitate the transportation of sodium ions. However, suffering from the slow kinetics and structural degradation, its rate performance is still not satisfied. Here, we report the fabrication of two types of Na0.44MnO2 hierarchical structures by optimized electrospinning and controlled subsequent annealing process. One is nanofiber (NF) which demonstrates a superior rate performance with reversible specific capacity of 69.5 mAh g-1 at 10 C, attributed to its one-dimensional (1D) ultralong and continuous fibrous network structure; the other is nanorod (NR) which exhibits an excellent cyclic performance with reversible specific capacity of 120 mAh g-1 after 140 cycles, due to its large S-shaped tunnel structure with a single crystalline structure.

  15. Nano-sized LiMn2O4 spinel cathode materials exhibiting high rate discharge capability for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Yingchao; Xie, Kai; Pan, Yi; Zheng, Chunman

    2011-08-01

    Nano-sized LiMn2O4 spinel with well crystallized homogeneous particles (60 nm) is synthesized by a resorcinol-formaldehyde route. Micro-sized LiMn2O4 spinel with micrometric particles (1 μm) is prepared by a conventional solid-state reaction. These two samples are characterized by XRD, SEM, TEM, BET, and electrochemical methods. At current rate of 0.2C (1C = 148 mA g-1), a discharge capacity of 136 mAh g-1 is obtained on the nano-sized LiMn2O4, which is higher than that of micro-sized one (103 mAh g-1). Furthermore, compared to the micro-sized sample, nano-sized LiMn2O4 shows much better rate capability, i.e. a capacity of 85 mAh g-1, 63% of that at 0.2C, is realized at 60C. The excellent high rate performance of nano-sized LiMn2O4 spinel may be attributed to its impurity-free nano-sized particles, higher surface area and well crystalline. The outstanding electrochemical performances demonstrate that the nano-sized LiMn2O4 spinel will be the promising cathode materials for high power lithium-ion batteries used in hybrid and electric vehicles.

  16. One-Pot Hydrothermal Synthesis of LiMn2O4 Cathode Material with Excellent High-Rate and Cycling Properties

    NASA Astrophysics Data System (ADS)

    Jiang, Qianqian; Wang, Xingyao; Zhang, Han

    2016-08-01

    The spinel LiMn2O4 was prepared by a one-step hydrothermal method using acetone as the reductant under different hydrothermal temperatures. X-ray diffraction and scanning electron microscopy analysis indicated that optimal LiMn2O4 particles (LMO-120) were synthesized at the temperature of 120°C and the particles were well distributed and about 410 nm in size. Electrochemical performance showed that the as-prepared LiMn2O4 particles exhibited a higher initial discharge capacity than commercial LiMn2O4 (131.5 mAh g-1 versus 115.6 mAh g-1 at 0.2 C). An excellent discharge capacity retention rate of 94.07% was observed after 60 charge-discharge cycles. On the other hand, when cycled at the high rate of 1 C, the optimal LiMn2O4 in this work showed a high discharge capacity of 107.5 mAh g-1 in contrast to only 92.3 mAh g-1 of the commercial LiMn2O4. These results indicate that LMO-120 showed excellent electrochemical performance, especially the prolonged cycling life and high-rate performance, which suggested that this spinel LiMn2O4 has promise for practical application as a high-rate cathode material for lithium ion batteries.

  17. Systematic investigation on Cadmium-incorporation in Li2FeSiO4/C cathode material for lithium-ion batteries

    PubMed Central

    Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

    2014-01-01

    Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li+-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material. PMID:24860942

  18. Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

    PubMed

    Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

    2015-10-14

    Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

  19. Orthorhombic Na[sub x]MnO[sub 2] as a cathode material for secondary sodium and lithium polymer batteries

    SciTech Connect

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Jonghe, L.C. de . Materials Sciences Div.)

    1994-11-01

    The use of orthorhombic Na[sub x]MnO[sub 2] as a cathode material for alkali metal polymer electrolyte batteries is described for the first time. This sodium manganese bronze has a tunnel structure and can reversibly intercalate up to 0.55 to 0.6 alkali metal ions (Li[sup +] or Na[sup +]) per manganese at moderate current densities, corresponding to capacities of 160 to 180 mAh/g. Li/PEO/Na[sub 0.2]Li[sub x]MnO[sub 2] cells [PEO = poly(ethylene oxide)] to date have been cycled over ninety times at 0.1 mA/cm[sup 2], with excellent capacity retention. Na/PEO/Na[sub x]MnO[sub 2] and Na[sub x]MnO[sub 2]/PEO/Na[sub x]MnO[sub 2] cells have been cycled over sixty times to date at the same rate, showing moderate capacity fading.

  20. In quest of cathode materials for Ca ion batteries: the CaMO3 perovskites (M = Mo, Cr, Mn, Fe, Co, and Ni).

    PubMed

    Arroyo-de Dompablo, M E; Krich, C; Nava-Avendaño, J; Palacín, M R; Bardé, F

    2016-07-20

    Basic electrochemical characteristics of CaMO3 perovskites (M = Mo, Cr, Mn, Fe, Co, and Ni) as cathode materials for Ca ion batteries are investigated using first principles calculations at the Density Functional Theory level (DFT). Calculations have been performed within the Generalized Gradient Approximation (GGA) and GGA+U methodologies, and considering cubic and orthorhombic perovskite structures for CaxMO3 (x = 0, 0.25, 0.5, 0.75 and 1). The analysis of the calculated voltage-composition profile and volume variations identifies CaMoO3 as the most promising perovskite compound. It combines good electronic conductivity, moderate crystal structure modifications, and activity in the 2-3 V region with several intermediate CaxMoO3 phases. However, we found too large barriers for Ca diffusion (around 2 eV) which are inherent to the perovskite structure. The CaMoO3 perovskite was synthesized, characterized and electrochemically tested, and results confirmed the predicted trends. PMID:27398629

  1. Extraction of manganese by alkyl monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-ion battery ternary cathodic material

    NASA Astrophysics Data System (ADS)

    Joo, Sung-Ho; Shin, Dongju; Oh, ChangHyun; Wang, Jei-Pil; Shin, Shun Myung

    2016-02-01

    We investigate the separation of manganese by an antagonistic effect from a leaching solution of ternary cathodic material of spent lithium-ion batteries that contain 11,400 mg L-1 Co, 11,700 mg L-1 Mn, 12,200 mg L-1 Ni, and 5300 mg L-1 Li using a mixture of alkyl monocarboxylic acid and di-(2-ethylhexyl)phosphoric acid extractants. pH isotherm, distribution coefficient, separation factor, McCabe-Thiele diagram, selective scrubbing, and countercurrent extraction tests are carried out to prove an antagonistic effect and to recover manganese using alkyl monocarboxylic in the mixed extractant. Slope analysis is used to determine the extraction mechanism between a mixture of extractants and valuable metals. An increasing concentration of alkyl monocarboxylic acid in the mixture of extractants results in a decrease in distribution coefficient of cobalt and manganese, however, the separation factor value (β(Mn/Co)) increases at pH 4.5. This is caused by slope analysis where alkyl monocarboxylic acid disrupts the extraction mechanism between di-(2-ethylhexyl)phosphoric acid and cobalt. Finally, continuous countercurrent extraction in a mini-plant test demonstrate the feasibility of manganese recovery from cobalt, nickel, and lithium.

  2. Systematic investigation on Cadmium-incorporation in Li2FeSiO4/C cathode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

    2014-05-01

    Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li+-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material.

  3. High-Rate and Cycling-Stable Nickel-Rich Cathode Materials with Enhanced Li(+) Diffusion Pathway.

    PubMed

    Tian, Jun; Su, Yuefeng; Wu, Feng; Xu, Shaoyu; Chen, Fen; Chen, Renjie; Li, Qing; Li, Jinghui; Sun, Fengchun; Chen, Shi

    2016-01-13

    The nickel-rich LiNi0.7Co0.15Mn0.15O2 material was sintered by Li source with the Ni0.7Co0.15Mn0.15(OH)2 precursor, which was prepared via hydrothermal treatment after coprecipitation. The intensity ratio of I(110)/I(108) obtained from X-ray diffraction patterns and high-resolution transmission electronmicroscopy confirm that the particles have enhanced growth of (110), (100), and (010) surface planes, which supply superior inherent Li(+) deintercalation/intercalation. The electrochemical measurement shows that the LiNi0.7Co0.15Mn0.15O2 material has high cycling stability and rate capability, along with fast charge and discharge ability. Li(+) diffusion coefficient at the oxidation peaks obtained by cyclic voltammogram measurement is as large as 10(-11) (cm(2) s(-1)) orders of magnitude, implying that the nickel-rich material has high Li(+) diffusion capability. PMID:26601895

  4. High-Rate and Cycling-Stable Nickel-Rich Cathode Materials with Enhanced Li(+) Diffusion Pathway.

    PubMed

    Tian, Jun; Su, Yuefeng; Wu, Feng; Xu, Shaoyu; Chen, Fen; Chen, Renjie; Li, Qing; Li, Jinghui; Sun, Fengchun; Chen, Shi

    2016-01-13

    The nickel-rich LiNi0.7Co0.15Mn0.15O2 material was sintered by Li source with the Ni0.7Co0.15Mn0.15(OH)2 precursor, which was prepared via hydrothermal treatment after coprecipitation. The intensity ratio of I(110)/I(108) obtained from X-ray diffraction patterns and high-resolution transmission electronmicroscopy confirm that the particles have enhanced growth of (110), (100), and (010) surface planes, which supply superior inherent Li(+) deintercalation/intercalation. The electrochemical measurement shows that the LiNi0.7Co0.15Mn0.15O2 material has high cycling stability and rate capability, along with fast charge and discharge ability. Li(+) diffusion coefficient at the oxidation peaks obtained by cyclic voltammogram measurement is as large as 10(-11) (cm(2) s(-1)) orders of magnitude, implying that the nickel-rich material has high Li(+) diffusion capability.

  5. Analysis of cathode geometry to minimize cathode erosion in direct current microplasma jet

    SciTech Connect

    Causa, Federica; Ghezzi, Francesco; Caniello, Roberto; Grosso, Giovanni; Dellasega, David

    2012-12-15

    Microplasma jets are now widely used for deposition, etching, and materials processing. The present study focuses on the investigation of the influence of cathode geometry on deposition quality, for microplasma jet deposition systems in low vacuum. The interest here is understanding the influence of hydrogen on sputtering and/or evaporation of the electrodes. Samples obtained with two cathode geometries with tapered and rectangular cross-sections have been investigated experimentally by scanning electron microscopy and energy dispersion X-ray spectroscopy. Samples obtained with a tapered-geometry cathode present heavy contamination, demonstrating cathode erosion, while samples obtained with a rectangular-cross-section cathode are free from contamination. These experimental characteristics were explained by modelling results showing a larger radial component of the electric field at the cathode inner wall of the tapered cathode. As a result, ion acceleration is larger, explaining the observed cathode erosion in this case. Results from the present investigation also show that the ratio of radial to axial field components is larger for the rectangular geometry case, thus, qualitatively explaining the presence of micro-hollow cathode discharge over a wide range of currents observed in this case. In the light of the above findings, the rectangular cathode geometry is considered to be more effective to achieve cleaner deposition.

  6. Analysis of cathode geometry to minimize cathode erosion in direct current microplasma jet

    NASA Astrophysics Data System (ADS)

    Causa, Federica; Ghezzi, Francesco; Dellasega, David; Caniello, Roberto; Grosso, Giovanni

    2012-12-01

    Microplasma jets are now widely used for deposition, etching, and materials processing. The present study focuses on the investigation of the influence of cathode geometry on deposition quality, for microplasma jet deposition systems in low vacuum. The interest here is understanding the influence of hydrogen on sputtering and/or evaporation of the electrodes. Samples obtained with two cathode geometries with tapered and rectangular cross-sections have been investigated experimentally by scanning electron microscopy and energy dispersion X-ray spectroscopy. Samples obtained with a tapered-geometry cathode present heavy contamination, demonstrating cathode erosion, while samples obtained with a rectangular-cross-section cathode are free from contamination. These experimental characteristics were explained by modelling results showing a larger radial component of the electric field at the cathode inner wall of the tapered cathode. As a result, ion acceleration is larger, explaining the observed cathode erosion in this case. Results from the present investigation also show that the ratio of radial to axial field components is larger for the rectangular geometry case, thus, qualitatively explaining the presence of micro-hollow cathode discharge over a wide range of currents observed in this case. In the light of the above findings, the rectangular cathode geometry is considered to be more effective to achieve cleaner deposition.

  7. Enhancing the Thermal and Upper Voltage Performance of Ni-Rich Cathode Material by a Homogeneous and Facile Coating Method: Spray-Drying Coating with Nano-Al2O3.

    PubMed

    Du, Ke; Xie, Hongbin; Hu, Guorong; Peng, Zhongdong; Cao, Yanbing; Yu, Fan

    2016-07-13

    The electrochemical performance of Ni-rich cathode material at high temperature (>50 °C) and upper voltage operation (>4.3 V) is a challenge for next-generation lithium-ion batteries (LIBs) because of the rapid capacity degradation over cycling. Here we report improved performance of LiNi0.8Co0.15Al0.05O2 materials via a LiAlO2 coating, which was prepared from a Ni0.80Co0.15Al0.05(OH)2 precursor by spray-drying coating with nano-Al2O3. Investigations by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy revealed that an Al2O3 layer is uniformly distributed on the precursor and a LiAlO2 layer on the as-prepared cathode material. Such a coating shell acts as a scavenger to protect the cathode material from attack by HF and serious side reactions, which remarkably enhances the cycle performance at 55 °C and upper operating voltage (4.4 and 4.5 V). In particular, the sample with a 2% Al2O3 coating shows capacity retentions of 90.40%, 85.14%, 87.85%, and 81.1% after 150 cycles at a rate of 1.0C at room temperature, 55 °C, 4.4 V, and 4.5 V, respectively, which are significantly higher than those of the pristine one. This is mainly due to the significant improvement of the structural stability led by the effective coating technique, which could be extended to other cathode materials to obtain LIBs with enhanced safety and excellent cycling stability.

  8. Cathodic protection -- Rectifier 47

    SciTech Connect

    Lane, W.M.

    1995-06-14

    This Acceptance Test Procedure (ATP) has been prepared to demonstrate that the cathodic protection system functions as required by project criteria. The cathodic protection system is for the tank farms at the Hanford Reservation. The tank farms store radioactive waste.

  9. Cathodic protection -- Rectifier 46

    SciTech Connect

    Lane, W.M.

    1995-06-14

    This Acceptance Test Procedure (ATP) has been prepared to demonstrate that the cathodic protection system functions as required by project criteria. The cathodic protection system is for the tank farms on the Hanford Reservation. The tank farms store radioactive waste.

  10. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries.

    PubMed

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-01-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4-δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4-δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn(3+) from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

  11. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-08-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4‑δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4‑δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF.

  12. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries.

    PubMed

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-01-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4-δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4-δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn(3+) from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF.

  13. Cathode for molten carbonate fuel cell

    DOEpatents

    Kaun, Thomas D.; Mrazek, Franklin C.

    1990-01-01

    A porous sintered cathode for a molten carbonate fuel cell and method of making same, the cathode including a skeletal structure of a first electronically conductive material slightly soluble in the electrolyte present in the molten carbonate fuel cell covered by fine particles of a second material of possibly lesser electronic conductivity insoluble in the electrolyte present in the molten carbonate fuel cell, the cathode having a porosity in the range of from about 60% to about 70% at steady-state cell operating conditions consisting of both macro-pores and micro-pores.

  14. An O3-type NaNi0.5Mn0.3Ti0.2O2 compound as new cathode material for room-temperature sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Gu, Minyi; Jiang, Jingyu; Lai, Chao; Ai, Xinping

    2016-09-01

    A single phase O3-type layered NaNi0.5Mn0.3Ti0.2O2 compound synthesized via simple solid-state reaction is first reported as a promising cathode material for sodium-ion batteries. A high reversible capacity of approximately 138 mAh g-1 and initial coulombic efficiency of above 96% can be obtained in half-cell. The performance of sodium-ion full-cells with NaNi0.5Mn0.3Ti0.2O2 as the cathode and presodiated hard carbon as the anodes were also evaluated. Based on the mass of cathode, the full-cells can still exhibit a high reversible capacity of ca. 131 mAh g-1. The prominent capacities make NaNi0.5Mn0.3Ti0.2O2 as an important cathode candidate for room temperature sodium-ion batteries.

  15. Micro hollow cathode discharges

    SciTech Connect

    Schoenbach, K.H.; Peterkin, F.E.; Verhappen, R.

    1995-12-31

    Hollow cathode discharges are glow discharges with the cathode fall and negative glow confined in a cavity in the cathode. For the discharge to develop, the cathode hole dimensions must be on the order of the mean free path. By reducing the cathode hole dimensions it is therefore possible to increase the pressure. Stable hollow cathode discharges in air have been observed at almost one atmosphere when the cathode diameter was reduced to 20 micrometers. In order to study the electrical parameters of a micro hollow cathode discharge, a set of experiments has been performed in argon at pressures in the torr range and a cathode hole diameter of 0.7 mm in molybdenum. The current-voltage characteristics and the appearance of the discharge plasma showed two distinct regions. At lower voltage or pressure the current varies linearly with voltage and the hollow cathode plasma is concentrated around the axis of the cathode hole (low glow mode). At higher values of voltage or pressure the current increases nonlinearly, up to a point where a transition into a low voltage hollow cathode arc was observed, and the plasma column expands and fills almost the entire cathode hole (high glow mode). Spectral measurements showed that the transition from the low glow mode into the high glow mode is related to an increased density of electrode vapor in the hollow cathode discharge. Up to the breakdown into a hollow cathode arc, the current voltage characteristic of the discharge has a positive slope. In this range, hollow cathode discharges can be operated in parallel without a ballast resistor.

  16. A Promising Na3V2(PO4)3/Ag + Graphene Composites as Cathode Material for Hybrid Lithium Batteries.

    PubMed

    Choi, Man-Soo; Kim, Hyun-Soo; Lee, Young-Moo; Lee, Sang-Min; Jin, Bong-Soo

    2015-11-01

    The NASICON (sodium super ionic conductor) based Na3V2(PO4)3/Ag + graphene (NVP/Ag + G) was successfully synthesized through a sol-gel route using a silver nitrate and graphene as a raw material. The effects of the physical and electrochemical properties of the NVP/Ag + G composites have been evaluated with X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and electrochemical measurements. The graphene and Ag significantly influenced the morphology, structure and electrochemical performance of the Na3V2(PO4)3 material. In the electrochemical measurement, the (NVP/Ag + G) electrode showed the discharge capacity of 102 mAh g(-1) at 0.1 C rate, which was higher than the pristine Na3V2(PO4). At a current rate of 5 C, it still exhibits the discharge capacity of 73 mAh g(-1) and the capacity retention of 71.6%. The results of higher electrochemical performance of the NVP/Ag + G composites are mainly attributed to the synergetic effect of the graphene and the silver particles. PMID:26726622

  17. Interplay between two-phase and solid solution reactions in high voltage spinel cathode material for lithium ion batteries

    SciTech Connect

    Xiao, Jie; Yu, Xiqian; Zheng, Jianming; Zhou, Yungang; Gao, Fei; Chen, Xilin; Bai, Jianming; Yang, Xiao-Qing; Zhang, Jiguang

    2013-06-06

    Lithium ion batteries (LIBs) are attracting intensive interests worldwide because of their potential applications in transportation electrification and utility grid. The intercalation compounds used in LIBs electrochemically react with Li+ ions via single or multiple phase transitions depending on the nature of the material structure as well as the synthesis and testing conditions. It is generally accepted that for high voltage spinel LiNi0.5Mn1.5O4, a promising candidate for LIBs, there are two successive two-phase reactions occurring during the delithiation/lithiation processes, as reflected by the two flat plateaus with a small step in between. Here we demonstrate, experimentally and theoretically, that through elemental substitution, each of the two-phase transitions has been largely converted into a solid solution reaction during the electrochemical process. The latter favors fast Li+ diffusion due to the reduced number of phase boundaries that Li+ ions have to overcome, as well as the reduced shrinkage of unit cells after charge. This work clearly elaborates one of the critical functions for element doping/substitution that has been widely adopted in the materials synthesis for LIBs, whose fundamental mechanisms are still obscured.

  18. [Effect of cathode material on electrolytic treatment of Acid Orange 7 by a three-phase three-dimensional electrode reactor].

    PubMed

    Xu, Li-Na; Zhao, Hua-zhang; Ni, Jin-ren

    2008-04-01

    The simulative wastewater containing Acid Orange 7 (AO7) of 300 mg/L was electrolytically treated by a three-phase three-dimensional electrode reactor. Particular attention was paid on the comparison of treatment efficiency of different cathodes in the system. Intermediate products and concentration of *OH and H2O2 were further investigated using HPLC, UV-Vis scan and GC-MS, with the purpose of investigating the electrolysis behavior of AO7 with different cathodes. Results showed that activated carbon fiber (ACF) cathode was more effective than graphite or stainless steel cathode. Despite all of the three investigated cathodes showed high efficiency in the decolorization of AO7 (more than 96% after 60 min of electrolysis under 20 V), the TOC removal ratio of ACF system (57.4%) was much higher than those of the other two. Although the generation of *OH and H2O2 were both found in the three systems, the concentration in the system with ACF as the cathode was much higher than those in the other two, which resulted in the better mineralization ability. Moreover, the same degradation route of AO7 was found in the three systems, which involved the generation of ketone and naphthol compounds.

  19. Pressed boride cathodes

    NASA Technical Reports Server (NTRS)

    Wolski, W.

    1985-01-01

    Results of experimental studies of emission cathodes made from lanthanum, yttrium, and gadolinium hexaborides are presented. Maximum thermal emission was obtained from lanthanum hexaboride electrodes. The hexaboride cathodes operated stably under conditions of large current density power draw, at high voltages and poor vacuum. A microtron electron gun with a lanthanum hexaboride cathode is described.

  20. Effect of Defects on Decay of Voltage and Capacity for Li[Li0.15Ni0.2Mn0.6]O2 Cathode Material.

    PubMed

    Yan, Wuwei; Liu, Yongning; Guo, Shengwu; Jiang, Tao

    2016-05-18

    Lithium-rich manganese metal layered oxides are very promising cathode materials for high-energy-density lithium-ion batteries, but improvement in voltage decay and capacity fade is a great challenge, which is mainly related to the structural instability or reconstruction of material's surface. Defects, such as part lattice distortions, local cation disordering and atomic ununiformity, often aggravate the further structural changes upon cycling. In this paper, we found that PEG contributed to form better layered structure, well crystallinity, uniform composition and polyhedral nanoparticles for Li[Li0.15Ni0.2Mn0.6]O2 (LNMO). On the basis of the comparative trial, a mechanism of electronegativity difference is proposed to elucidate cation nonuniform distribution. Higher electronegativity of Ni (1.91) than Mn (1.55) show a stronger ability of attraction between Ni and O atoms, and then led to Ni atoms show stronger diffusion driving force toward particle surface to contact the rich O atoms during sintering in air. However, PEG polymer can form a better barrier for more O atoms to attract Ni and Mn atoms on particle surface so that facilitated a uniform distribution. The electrochemical test indicated that the decay of discharge capacity and working voltage was mitigated, which was identified by the result of HRTEM analysis that the initial less defect structure obviously retarded the phase transformation from the layered to spinel after 50 cycles. Therefore, defects are crucial for understanding the voltage fade and capacity decay, and the improvement of performance also demonstrates that designing optimum compositions and ordering atomic arrangements will contribute to stabilize the surface structure and restrain inherent phase transitions. PMID:27116571

  1. Ca and In co-doped BaFeO3-δ as a cobalt-free cathode material for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Lam, Kwun Yu; Saccoccio, Mattia; Gao, Yang; Chen, Dengjie; Ciucci, Francesco

    2016-08-01

    We report Ba0·95Ca0·05Fe0·95In0·05O3-δ (BCFI), a novel cobalt-free perovskite, as a promising cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). We synthesize this new material, and systematically characterize its lattice structure, thermal stability, chemical composition, electrical conductivity, and oxygen reduction reaction (ORR) activity. The cubic phase of BaFeO3-δ is stabilized by light isovalent and lower-valence substitution, i.e., 5% Ca2+ in the Ba2+ site and 5% In3+ in the Fe3+/Fe4+ site, in contrast with the typical approach of substituting elements of higher valence. Without resorting to co-doping strategy, the phase of BaFe0·95In0·05O3-δ (BFI) is rhombohedral, while Ba0·95Ca0·05FeO3-δ (BCF) is a mixture of the cubic phase together with BaFe2O4 impurities. The structure of BCFI is cubic from room temperature up to 900 °C with a moderate thermal expansion coefficient of 23.2 × 10-6 K-1. Thanks to the large oxygen vacancy concentration and fast oxygen mobility, BCFI exhibits a favorable ORR activity, i.e., we observe a polarization resistance as small as 0.038 Ω cm2 at 700 °C. The significantly enhanced performance, compared with BFI and BCF, is attributed to the presence of the cubic phase and the large oxygen vacancies brought by the isovalent substitution in the A-site and lower-valence doping in the B-site.

  2. Ca and In co-doped BaFeO3-δ as a cobalt-free cathode material for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Lam, Kwun Yu; Saccoccio, Mattia; Gao, Yang; Chen, Dengjie; Ciucci, Francesco

    2016-08-01

    We report Ba0·95Ca0·05Fe0·95In0·05O3-δ (BCFI), a novel cobalt-free perovskite, as a promising cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). We synthesize this new material, and systematically characterize its lattice structure, thermal stability, chemical composition, electrical conductivity, and oxygen reduction reaction (ORR) activity. The cubic phase of BaFeO3-δ is stabilized by light isovalent and lower-valence substitution, i.e., 5% Ca2+ in the Ba2+ site and 5% In3+ in the Fe3+/Fe4+ site, in contrast with the typical approach of substituting elements of higher valence. Without resorting to co-doping strategy, the phase of BaFe0·95In0·05O3-δ (BFI) is rhombohedral, while Ba0·95Ca0·05FeO3-δ (BCF) is a mixture of the cubic phase together with BaFe2O4 impurities. The structure of BCFI is cubic from room temperature up to 900 °C with a moderate thermal expansion coefficient of 23.2 × 10-6 K-1. Thanks to the large oxygen vacancy concentration and fast oxygen mobility, BCFI exhibits a favorable ORR activity, i.e., we observe a polarization resistance as small as 0.038 Ω cm2 at 700 °C. The significantly enhanced performance, compared with BFI and BCF, is attributed to the presence of the cubic phase and the large oxygen vacancies brought by the isovalent substitution in the A-site and lower-valence doping in the B-site.

  3. Effect of Defects on Decay of Voltage and Capacity for Li[Li0.15Ni0.2Mn0.6]O2 Cathode Material.

    PubMed

    Yan, Wuwei; Liu, Yongning; Guo, Shengwu; Jiang, Tao

    2016-05-18

    Lithium-rich manganese metal layered oxides are very promising cathode materials for high-energy-density lithium-ion batteries, but improvement in voltage decay and capacity fade is a great challenge, which is mainly related to the structural instability or reconstruction of material's surface. Defects, such as part lattice distortions, local cation disordering and atomic ununiformity, often aggravate the further structural changes upon cycling. In this paper, we found that PEG contributed to form better layered structure, well crystallinity, uniform composition and polyhedral nanoparticles for Li[Li0.15Ni0.2Mn0.6]O2 (LNMO). On the basis of the comparative trial, a mechanism of electronegativity difference is proposed to elucidate cation nonuniform distribution. Higher electronegativity of Ni (1.91) than Mn (1.55) show a stronger ability of attraction between Ni and O atoms, and then led to Ni atoms show stronger diffusion driving force toward particle surface to contact the rich O atoms during sintering in air. However, PEG polymer can form a better barrier for more O atoms to attract Ni and Mn atoms on particle surface so that facilitated a uniform distribution. The electrochemical test indicated that the decay of discharge capacity and working voltage was mitigated, which was identified by the result of HRTEM analysis that the initial less defect structure obviously retarded the phase transformation from the layered to spinel after 50 cycles. Therefore, defects are crucial for understanding the voltage fade and capacity decay, and the improvement of performance also demonstrates that designing optimum compositions and ordering atomic arrangements will contribute to stabilize the surface structure and restrain inherent phase transitions.

  4. Microwave-enhanced electrochemical cycling performance of the LiNi0.2Mn1.8O4 spinel cathode material at elevated temperature.

    PubMed

    Raju, Kumar; Nkosi, Funeka P; Viswanathan, Elumalai; Mathe, Mkhulu K; Damodaran, Krishnan; Ozoemena, Kenneth I

    2016-05-14

    The well-established poor electrochemical cycling performance of the LiMn2O4 (LMO) spinel cathode material for lithium-ion batteries at elevated temperature stems from the instability of the Mn(3+) concentration. In this work, a microwave-assisted solid-state reaction has been used to dope LMO with a very low amount of nickel (i.e., LiNi0.2Mn1.8O4, herein abbreviated as LMNO) for lithium-ion batteries from Mn3O4 which is prepared from electrolytic manganese oxide (EMD, γ-MnO2). To establish the impact of microwave irradiation on the electrochemical cycling performance at an elevated temperature (60 °C), the Mn(3+) concentration in the pristine and microwave-treated LMNO samples was independently confirmed by XRD, XPS, (6)LiMAS-NMR and electrochemical studies including electrochemical impedance spectroscopy (EIS). The microwave-treated sample (LMNOmic) allowed for the clear exposure of the {111} facets of the spinel, optimized the Mn(3+) content, promoting structural and cycle stability at elevated temperature. At room temperature, both the pristine (LMNO) and microwave-treated (LMNOmic) samples gave comparable cycling performance (>96% capacity retention and ca. 100% coulombic efficiency after 100 consecutive cycling). However, at an elevated temperature (60 °C), the LMNOmic gave an improved cycling stability (>80% capacity retention and ca. 90% coulombic efficiency after 100 consecutive cycling) compared to the LMNO. For the first time, the impact of microwave irradiation on tuning the average manganese redox state of the spinel material to enhance the cycling performance of the LiNi0.2Mn1.8O4 at elevated temperature and lithium-ion diffusion kinetics has been clearly demonstrated.

  5. Microwave-enhanced electrochemical cycling performance of the LiNi0.2Mn1.8O4 spinel cathode material at elevated temperature.

    PubMed

    Raju, Kumar; Nkosi, Funeka P; Viswanathan, Elumalai; Mathe, Mkhulu K; Damodaran, Krishnan; Ozoemena, Kenneth I

    2016-05-14

    The well-established poor electrochemical cycling performance of the LiMn2O4 (LMO) spinel cathode material for lithium-ion batteries at elevated temperature stems from the instability of the Mn(3+) concentration. In this work, a microwave-assisted solid-state reaction has been used to dope LMO with a very low amount of nickel (i.e., LiNi0.2Mn1.8O4, herein abbreviated as LMNO) for lithium-ion batteries from Mn3O4 which is prepared from electrolytic manganese oxide (EMD, γ-MnO2). To establish the impact of microwave irradiation on the electrochemical cycling performance at an elevated temperature (60 °C), the Mn(3+) concentration in the pristine and microwave-treated LMNO samples was independently confirmed by XRD, XPS, (6)LiMAS-NMR and electrochemical studies including electrochemical impedance spectroscopy (EIS). The microwave-treated sample (LMNOmic) allowed for the clear exposure of the {111} facets of the spinel, optimized the Mn(3+) content, promoting structural and cycle stability at elevated temperature. At room temperature, both the pristine (LMNO) and microwave-treated (LMNOmic) samples gave comparable cycling performance (>96% capacity retention and ca. 100% coulombic efficiency after 100 consecutive cycling). However, at an elevated temperature (60 °C), the LMNOmic gave an improved cycling stability (>80% capacity retention and ca. 90% coulombic efficiency after 100 consecutive cycling) compared to the LMNO. For the first time, the impact of microwave irradiation on tuning the average manganese redox state of the spinel material to enhance the cycling performance of the LiNi0.2Mn1.8O4 at elevated temperature and lithium-ion diffusion kinetics has been clearly demonstrated. PMID:27113855

  6. A Comparison of the Effects of Information Mapped Learning Materials and Traditional Materials on the Learning of Concepts via the Printed Page and Computer Cathode Ray Tube.

    ERIC Educational Resources Information Center

    Geisert, Paul

    A study was made of the learning effects of information mapping; i.e., the technique of organizing materials on the printed page in a format which clearly illustrates the order and organization of the materials. The investigation of the effects of information mapping and information-mapped feedback on achievement, time variables, and attitude…

  7. Hollow Li1.2Mn0.5Co0.25Ni0.05O2 microcube prepared by binary template as a cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Shi, S. J.; Lou, Z. R.; Xia, T. F.; Wang, X. L.; Gu, C. D.; Tu, J. P.

    2014-07-01

    Novel Li1.2Mn0.5Co0.25Ni0.05O2 microcube is prepared through a simple binary template method. After calcined at 800 °C, lithium and nickel are permeated into the cathode material and a well-crystallized Li-rich layered oxide is obtained. Furthermore, hollow circle cube architecture is formed due to the decomposing of the carbonate. As a cathode material for lithium ion batteries (LIBs), the oxide with such architecture can deliver high initial discharge capacity of 272.9 mAh g-1 at a current density of 20 mA g-1. High reversible discharge capacities of 208 mAh g-1 and 110 mAh g-1 are obtained at a current density of 200 mA g-1 and 2000 mA g-1, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are performed to further study the hollow Li1.2Mn0.5Co0.25Ni0.05O2 microcube. It is remarkable that such architecture makes the Li-rich layered oxide Li1.2Mn0.5Co0.25Ni0.05O2 a promising cathode material for LIBs.

  8. Structural and electronic properties of Li-ion battery cathode material MoF{sub 3} from first-principles

    SciTech Connect

    Li, A.Y.; Wu, S.Q.; Yang, Y.; Zhu, Z.Z.

    2015-07-15

    The transition metal fluorides have been extensively investigated recently as the electrode materials with high working voltage and large capacity. The structural, electronic and magnetic properties of MoF{sub 3} are studied by the first-principles calculations within both the generalized gradient approximation (GGA) and GGA+U frameworks. Our results show that the antiferromagnetic configuration of MoF{sub 3} is more stable than the ferromagnetic one, which is consistent with experimental results. The analysis of the electronic density of states shows that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap, which is similar to the case of FeF{sub 3}. Moreover, small spin polarizations were found on the sites of fluorine ions, which accords with a fluorine-mediated superexchange mechanism for the Mo–Mo magnetic interaction. - Graphical abstract: Deformation charge density and spin-density for MoF{sub 3} in the AF configuration. - Highlights: • The ground state of MoF{sub 3} is shown to be antiferromagnetic, in consistent with experiments. • The electronic states show that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap. • A fluorine-mediated super-exchange mechanism for the Mo–Mo magnetic interaction is shown.

  9. Inert Anode/Cathode Program: Fiscal Year 1986 annual report. [For Hall-Heroult cells

    SciTech Connect

    Brenden, B.B.; Davis, N.C.; Koski, O.H.; Marschman, S.C.; Pool, K.H.; Schilling, C.H.; Windisch, C.F.; Wrona, B.J.

    1987-06-01

    Purpose of the program is to develop long-lasting, energy-efficient anodes, cathodes, and ancillary equipment for Hall-Heroult cells used by the aluminum industry. The program is divided into four tasks: Inert Anode Development, Cathode Materials Evaluation, Cathode Bonding Development, and Sensor Development. To devise sensors to control the chemistry of Hall-Heroult cells using stable anodes and cathodes. This report highlights the major FY86 technical accomplishments, which are presented in the following sections: Management, Materials Development, Materials Evaluation, Thermodynamic Evaluation, Laboratory Cell Tests, Large-Scale Tests, Cathode Materials Evaluation, Cathode Bonding Development, and Sensor Development.

  10. Microwave solid-state synthesis of LiV(3)O(8) as cathode material for lithium batteries.

    PubMed

    Yang, Gang; Wang, Guan; Hou, Wenhua

    2005-06-01

    A novel and economical microwave route has been developed for the synthesis of electrochemically active LiV(3)O(8) material by using a domestic microwave oven. The heating behavior of the designed reaction system guided the preparation of LiV(3)O(8) at a suitable irradiation power (i.e. heating rate), reaction time, and temperature. At the lowest irradiation power, the conversion fraction of reactants was mainly controlled by reaction temperature. Characterization results of X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopy, scanning (SEM) and transmission (TEM) electron microscopy, and BET surface areas indicated that the phases of samples prepared by microwave and traditional methods were in good agreement. Nevertheless, the crystallinity, crystallite configuration, and morphology of the samples were different, and were affected by the irradiation time and power. A floppy superposition structure of nanosheets (the size of one nanosheet was about 4.5 microm x 1.2 microm x 3 nm) was preferentially grown at the lowest irradiation power, and this effect on structure was more in evidence as the nanorods formed at the highest irradiation power. Electrochemical studies on ionic conductivity, electrochemical impedance spectroscopy (EIS), and charge-discharge capacity were carried out. It was found that the conductivity, first discharge capacity, and cycle performances of the samples were affected by the crystal size, crystallinity, and crystal configuration and defection concentration. The sample L30 prepared at the lowest irradiation power and the shortest time (30 min) showed the highest discharge capacity (335 mAh/g), but its discharge capacity decreased rapidly. By comparison, the sample L100 had a floppy superposition structure of nanosheets and a high surface area, provided a good two-dimensional channel for the transition of Li(+) ions, and was stable during the intercalation/deintercalation process of Li(+) ions, therefore the high

  11. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X. S.

    2013-12-01

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg2+ doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg2+ doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li+ diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg2+ doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of ``cushion'' as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co

  12. Long lifetime hollow cathodes for 30-cm mercury ion thrusters

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Kerslake, W. R.

    1976-01-01

    An experimental investigation of hollow cathodes for 30-cm Hg bombardment thrusters was carried out. Both main and neutralizer cathode configurations were tested with both rolled foil inserts coated with low work function material and impregnated porous tungsten inserts. Temperature measurements of an impregnated insert at various positions in the cathode were made. These, along with the cathode thermal profile are presented. A theory for rolled foil and impregnated insert operation and lifetime in hollow cathodes is developed. Several endurance tests, as long as 18000 hours at emission currents of up to 12 amps were attained with no degradation in performance.

  13. Lithium difluoro(oxalate)borate and LiBF4 blend salts electrolyte for LiNi0.5Mn1.5O4 cathode material

    NASA Astrophysics Data System (ADS)

    Zhou, Hongming; Xiao, Kaiwen; Li, Jian

    2016-01-01

    The electrochemical behaviors of lithium difluoro(oxalate)borate (LiODFB) and LiBF4 blend salts in ethylene carbonate + dimethyl carbonate + ethyl(methyl) carbonate (EC + DMC + EMC, 1:1:1, by wt.) have been investigated for LiNi0.5Mn1.5O4 cathode in lithium-ion batteries. The electric conductivity tests are utilized to examine the relationship among solution conductivity, the electrolyte composition and temperature. Through cyclic voltammetry, charge-discharge test and AC impedance measurements, we compare the capacity and cycling efficiency of LNMO cathode in different electrolyte systems at different temperatures and discharge current rates. Scanning electron microscopy (SEM) analysis and X-ray photoelectron spectroscopy (XPS) are served to analyze the surface nature of LNMO cathode after cycles at elevated temperature. These results demonstrate that LNMO cathode can exert excellent electrochemical performance with the increase of LiODFB concentration at room temperature and elevated temperature and it is found that just slight LiBF4, mixed with LiODFB as blend salts, can strikingly improve the cyclability at -20 °C, especially in high-rate cycling. Grouped together, the optimum LiODFB/LiBF4 molar ratio is around 4:1, which can present an excellent affinity to LNMO cathode in a wide electrochemical window.

  14. Li2S@C composite incorporated into 3D reduced graphene oxide as a cathode material for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Wang, D. H.; Xie, D.; Yang, T.; Zhong, Y.; Wang, X. L.; Xia, X. H.; Gu, C. D.; Tu, J. P.

    2016-05-01

    Surface conductive engineering on Li2S is critical for construction of advanced cathodes of lithium-sulfur batteries. Herein, we construct a high-performance Li2S-based composite cathode with the help of three-dimensional reduced graphene oxide (3D-rGO) network and outer carbon coating. Typically, the Li2S@C particles are uniformly embedded into 3D-rGO to form a binder-free 3D-rGO-Li2S@C cathode by the combination of a liquid solution-evaporation coating and PVP (Polyvinyl Pyrrolidone) carbonization. The 3D-rGO-Li2S@C cathode exhibits a high initial discharge capacity of 856 mAh g-1 at 0.1C, superior cycling stability with a capacity of 388.4 mAh g-1 after 200 cycles at 1C, corresponding to a low capacity fading rate. It is demonstrated that the outer conductive coating is effective and necessary for electrochemical enhancement of Li2S cathodes by improving electrical conductivity and prohibiting polysulfide from shuttling during cycling.

  15. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries.

    PubMed

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X S

    2014-01-21

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.

  16. Growth mechanism and magnetic and electrochemical properties of Na{sub 0.44}MnO{sub 2} nanorods as cathode material for Na-ion batteries

    SciTech Connect

    Demirel, S.; Oz, E.; Altin, E.; Altin, S.; Bayri, A.; Kaya, P.; Turan, S.; Avci, S.

    2015-07-15

    Nanorods of Na{sub 0.44}MnO{sub 2} are a promising cathode material for Na-ion batteries due to their large surface area and single crystalline structure. We report the growth mechanism of Na{sub 0.44}MnO{sub 2} nanorods via solid state synthesis and their physical properties. The structure and the morphology of the Na{sub 0.44}MnO{sub 2} nanorods are investigated by X-ray diffraction (XRD), scanning and tunneling electron microscopy (SEM and TEM), and energy-dispersive X-ray (EDX) techniques. The growth mechanism of the rods is investigated and the effects of vapor pressure and partial melting of Na-rich regions are discussed. The magnetic measurements show an antiferromagnetic phase transition at 25 K and the μ{sub eff} is determined as 3.41 and 3.24 μ{sub B} from the χ–T curve and theoretical calculation, respectively. The electronic configuration and spin state of Mn{sup 3+} and Mn{sup 4+} are discussed in detail. The electrochemical properties of the cell fabricated using the nanorods are investigated and the peaks in the voltammogram are attributed to the diffusion of Na ions from different sites. Na intercalation process is explained by one and two Margules and van Laar models. - Highlights: • We synthesized Na{sub 0.44}MnO{sub 2} nanorods via a simple solid state reaction technique. • Our studies show that excess Na plays a crucial role in the nanorod formation. • Magnetization measurements show that Mn{sup 3+} ions are in LS and HS states. • The electrochemical properties of the cell fabricated using the nanorods are investigated. • Na intercalation process is explained by one and two Margules and van Laar models.

  17. Robust NdBa0.5Sr0.5Co1.5Fe0.5O5+δ cathode material and its degradation prevention operating logic for intermediate temperature-solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Lee, Tae-Hee; Park, Ka-Young; Kim, Nam-In; Song, Sun-Ju; Hong, Ki-Ha; Ahn, Docheon; Azad, Abul K.; Hwang, Junyeon; Bhattacharjee, Satadeep; Lee, Seung-Cheol; Lim, Hyung-Tae; Park, Jun-Young

    2016-11-01

    We report solutions (durable material and degradation prevention method) to minimize the performance degradation of cell components occurring in the solid oxide fuel cell (SOFC) operation. Reliability testing is carried out with the Nisbnd Nd0.1Ce0.9O2-δ (NDC) anode-supported intermediate temperature-SOFCs. For the cathode materials, single perovskite structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) and double perovskite structured NdBa0.5Sr0.5Co1.5Fe0.5O5+δ (NBSCF) are prepared and evaluated under harsh SOFC operating conditions. The double perovskite NBSCF cathode shows excellent stability in harsh SOFC environments of high humidity and low flow rate of air. Furthermore, we propose the concurrent fuel and air starvation mode, in which the cell potential is temporarily reduced due to the formation of both fuel-starvation (in the anode) and air-depletion (in the cathode) concurrently under a constant load. This is carried out in order to minimize the performance decay of the stable NBSCF-cell through the periodic and extra reduction of aH2 O (and aO2) in the anode. The operating-induced degradation of SOFCs, which are ordinarily assumed to be unrecoverable, can be completely circumvented by the proposed periodical operation logic to prevent performance degradation (concurrent fuel-starvation and air-depletion mode).

  18. Surface stability of spinel MgNi0.5Mn1.5O4 and MgMn2O4 as cathode materials for magnesium ion batteries

    NASA Astrophysics Data System (ADS)

    Jin, Wei; Yin, Guangqiang; Wang, Zhiguo; Fu, Y. Q.

    2016-11-01

    Rechargeable ion batteries based on the intercalation of multivalent ions are attractive due to their high energy density and structural stability. Surface of cathode materials plays an important role for the electrochemical performance of the rechargeable ion batteries. In this work we calculated surface energies of (001), (110) and (111) facets with different terminations in spinel MgMn2O4 and MgNi0.5Mn1.5O4 cathodes. Results showed clearly that atomic reconstruction occurred due to surface relaxation. The surface energies for the (001), (110) and (111) surfaces of the MgNi0.5Mn1.5O4 were 0.08, 0.13 and 0.11 J/m2, respectively, whereas those of the Ni-doped MgMn2O4 showed less dependence on the surface structures.

  19. Lithiated vanadium oxide (LVO), gamma-lithium vanadium bronze (gamma-LiV2O5) and vanadium dioxide (Vo2) as thermal-battery cathode materials. Technical report

    SciTech Connect

    Richie, A.G.; Warner, K.

    1991-05-01

    Thermal batteries are high temperature reserve batteries, predominantly used in missiles. Modern designs use a lithium (or lithium alloy) anode, an immobilized molten salt electrolyte and an iron-disulphide cathode. These batteries have many advantages: high reliability, long storage life without maintenance, wide temperature range of operation and, sometimes, high power. However, the energy density is rather low and this could be improved if the individual cell voltage could be raised above the present 2.2 V/cell open circuit-voltage for the lithium iron-disulphide couple. A new cathode material, lithiated vanadium oxide (LVO), been invented at RAE with the advantage of the much higher open-circuit voltage of 2.6 V/cell versus lithium. The properties of LVO have been investigated and it has been shown that LVO consists of vanadium dioxide as the major component. Some lithium bromide is also present.

  20. Plasma distribution of cathodic ARC deposition system

    SciTech Connect

    Anders, S.; Raoux, S.; Krishnan, K.; MacGill, R.A.; Brown, I.G.

    1996-08-01

    The plasma distribution using a cathodic arc plasma source with and without magnetic macroparticle filter has been determined by depositing on a transparent plastic substrate and measuring the film absorption. It was found that the width of the distribution depends on the arc current, and it also depends on the cathode material which leads to a spatial separation of the elements when an alloy cathode is used. By applying a magnetic multicusp field near the exit of the magnetic filter, it was possible to modify the plasma distribution and obtain a flat plasma profile with a constant and homogeneous elemental distribution.

  1. High pressure microhollow cathode discharges in air

    SciTech Connect

    Khedr, M.A.; Stark, R.H.; Watson, B.; Schoenbach, K.H.

    1998-12-31

    Research on high pressure, large volume glow discharges in air is motivated by applications such as reflectors and absorbers for electromagnetic radiation, plasma processing, and the remediation of gaseous pollution. In order to prevent glow-to-arc transitions, which in high-pressure glow discharges start in the cathode region, it is proposed to use a plasma cathode consisting of an array of microhollow cathode discharges. To explore the conditions for stable operation of single 100 {micro}m microhollow cathode discharges in flowing air, the current-voltage characteristics, and the visual appearance of a 100 {micro}m microhollow cathode discharge were studied. The results show that the threshold current for the transition from a glow into a filamentary discharge varies inversely with pressure. At pressures of 400 Torr the current in the 100 {micro}m hollow cathode discharge must not exceed 0.5 mA in order for the discharge to be stable. The type of instability, which causes the transition from dc to fluctuating currents, is not known at this time, but the observed dependence of the threshold current from the gas pressure points to a thermal instability. Assuming that the White-Allis scaling law still holds for air discharges at pressures close to atmospheric, it is expected that reducing the cathode hole diameter to 50 {micro}m will allow us to operate microhollow cathode discharges at atmospheric air with currents of up to 0.25 mA. Experimental studies on the effect of the cathode dimensions and cathode material are underway and results will be discussed at the conference.

  2. Molten carbonate fuel cell cathode with mixed oxide coating

    DOEpatents

    Hilmi, Abdelkader; Yuh, Chao-Yi

    2013-05-07

    A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

  3. Praseodymium-deficiency Pr0.94BaCo2O6-δ double perovskite: A promising high performance cathode material for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Meng, Fuchang; Xia, Tian; Wang, Jingping; Shi, Zhan; Zhao, Hui

    2015-10-01

    Praseodymium-deficiency Pr0.94BaCo2O6-δ (P0.94BCO) double perovskite has been evaluated as a cathode material for intermediate-temperature solid oxide fuel cells. X-ray diffraction pattern shows the orthorhombic structure with double lattice parameters from the primitive perovskite cell in Pmmm space group. P0.94BCO has a good chemical compatibility with Ce0.9Gd0.1O1.95 (CGO) electrolyte even at 1000 °C for 24 h. It is observed that the Pr-deficiency can introduce the extra oxygen vacancies in P0.94BCO, further enhancing its electrocatalytic activity for oxygen reduction reaction. P0.94BCO demonstrates the promising cathode performance as evidenced by low polarization are-specific resistance (ASR), e. g. 0.11 Ω cm2 and low cathodic overpotential e. g. -56 mV at a current density of -78 mA cm-2 at 600 °C in air. These features are comparable to those of the benchmark cathode Ba0.5Sr0.5Co0.8Fe0.2O3-δ. The fuel cell CGO-Ni|CGO|P0.94BCO presents the attractive peak power density of 1.05 W cm-2 at 600 °C. Furthermore, the oxygen reduction kinetics of P0.94BCO material is also investigated, and the rate-limiting steps for oxygen reduction reaction are determined.

  4. Nickel-titanium-phosphate cathodes

    DOEpatents

    Belharouak, Ilias; Amine, Khalil

    2008-12-16

    Cathode materials having an improved electronic conductivity allowing for faster kinetics in the electrochemical reaction, as well as higher conductivity to meet the power requirements for many consumer applications, especially at low temperatures. The cathode material comprises a compound from the family of compounds where the basic unit is generally represented by Li.sub.xNi.sub.0.5TiOPO.sub.4. The structure of Li.sub.xNi.sub.0.5TiOPO.sub.4 includes corner sharing octahedra [TiO.sub.6] running along the C-axis. The structure is such that nearly three Li atoms are being inserted in Li.sub.xNi.sub.0.5TiOPO.sub.4. A cell in accordance with the principles of the present invention is rechargable and demonstrates a high capacity of lithium intercalation and fast kinetics.

  5. Parallel operation of microhollow cathode discharges

    SciTech Connect

    Shi, W.; Stark, R.H.; Schoenbach, K.H.

    1999-02-01

    Parallel operation of dc microhollow cathode discharges in argon at pressures up to several hundred torr was obtained without individual ballast at low currents, where the slope of the current-voltage characteristic is positive. By using semi-insulating silicon as anode material, the authors were able to extend the range of stable operation over the entire current range, including that with negative differential resistance. This opens the possibility to utilize microhollow cathode discharge arrays in flat panel lamps.

  6. Cathode R&D for future light sources.

    SciTech Connect

    Dowell, D. H.; Bazarov, I.; Dunham, B.; Harkay, K.; Hernandez-Garcia, C.; Legg, R.; Padmore, H.; Rao, T.; Smedley, J.; Wan, W.; Accelerator Systems Division; SLAC National Accelerator Lab.; Cornell Univ.; Thomas Jefferson Lab.; Univ. of Wisconsin; LBNL; BNL

    2010-03-18

    This paper reviews the requirements and current status of cathodes for accelerator applications, and proposes a research and development plan for advancing cathode technology. Accelerator cathodes need to have long operational lifetimes and produce electron beams with a very low emittance. The two principal emission processes to be considered are thermionic and photoemission with the photocathodes being further subdivided into metal and semi-conductors. Field emission cathodes are not included in this analysis. The thermal emittance is derived and the formulas used to compare the various cathode materials. To date, there is no cathode which provides all the requirements needed for the proposed future light sources. Therefore a three part research plan is described to develop cathodes for these future light source applications.

  7. Cathode R&D for Future Light Sources

    SciTech Connect

    Dowell, D.H.; Bazarov, I.; Dunham, B.; Harkay, K.; Hernandez-Garcia; Legg, R.; Padmore, H.; Rao, T.; Smedley, J.; Wan, W.; /LBL, Berkeley

    2010-05-26

    This paper reviews the requirements and current status of cathodes for accelerator applications, and proposes a research and development plan for advancing cathode technology. Accelerator cathodes need to have long operational lifetimes and produce electron beams with a very low emittance. The two principal emission processes to be considered are thermionic and photoemission with the photocathodes being further subdivided into metal and semi-conductors. Field emission cathodes are not included in this analysis. The thermal emittance is derived and the formulas used to compare the various cathode materials. To date, there is no cathode which provides all the requirements needed for the proposed future light sources. Therefore a three part research plan is described to develop cathodes for these future light source applications.

  8. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

    PubMed Central

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-01-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

  9. LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

    SciTech Connect

    Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

    2002-03-31

    This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves as the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest ASR is

  10. Preparation and Electrochemical Performance of LiNi1/3Co1/3Mn1/3O2 Cathode Materials for Lithium-ion Batteries from Spent Mixed Alkaline Batteries

    NASA Astrophysics Data System (ADS)

    Yang, Li; Xi, Guoxi

    2016-01-01

    LiNi1/3Co1/3Mn1/3O2 cathode materials of lithium-ion batteries were successfully re-synthesized using mixed spent alkaline zinc-manganese batteries and spent lithium-ion batteries as the raw materials. These materials were synthesized by using a combination of dissolution, co-precipitation, calcination, battery preparation, and battery charge-discharge processes. The phase composition, morphology, and electrochemical performance of the products were determined by inductively coupled plasma optical emission spectroscopy, infrared spectra, x-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, and charge-discharge measurements. The results showed that LiNi1/3Co1/3Mn1/3O2 cathode materials could be successfully re-synthesized at optimal preparation conditions of: co-precipitation, pH value of 8, calcination temperature of 850°C, and calcination time of 10 h. Furthermore, the electrochemical results showed that the re-synthesized sample could deliver an initial discharge capacity of up to 160.2 mAh g-1 and Coulomb efficiency of 99.8%.

  11. Cathode refunctionalization as a lithium ion battery recycling alternative

    NASA Astrophysics Data System (ADS)

    Ganter, Matthew J.; Landi, Brian J.; Babbitt, Callie W.; Anctil, Annick; Gaustad, Gabrielle

    2014-06-01

    An approach to battery end-of-life (EOL) management is developed involving cathode refunctionalization, which enables remanufacturing of the cathode from EOL materials to regain the electrochemical performance. To date, the optimal end-of-life management of cathode materials is based on economic value and environmental impact which can influence the methods and stage of recycling. Traditional recycling methods can recover high value metal elements (e.g. Li, Co, Ni), but still require synthesis of new cathode from a mix of virgin and recovered materials. Lithium iron phosphate (LiFePO4) has been selected for study as a representative cathode material due to recent mass adoption and limited economic recycling drivers due to the low inherent cost of iron. Refunctionalization of EOL LiFePO4 cathode was demonstrated through electrochemical and chemical lithiation methods where the re-lithiated LiFePO4 regained the original capacity of 150-155 mAh g-1. The environmental impact of the new recycling technique was determined by comparing the embodied energy of cathode material originating from virgin, recycled, and refunctionalized materials. The results demonstrate that the LiFePO4 refunctionalization process, through chemical lithiation, decreases the embodied energy by 50% compared to cathode production from virgin materials.

  12. Alternative cathodes for molten carbonate fuel cells

    SciTech Connect

    Bloom, I.; Lanagan, M.; Roche, M.F.; Krumpelt, M.

    1996-02-01

    Argonne National Laboratory (ANL) is developing advanced cathodes for pressurized operation of the molten carbonate fuel cell (MCFC). The present cathode, lithiated nickel oxide, tends to transport to the anode of the MCFC, where it is deposited as metallic nickel. The rate of transport increases with increasing CO{sub 2} pressure. This increase is due to an increased solubility of nickel oxide (NiO) in the molten carbonate electrolyte. An alternative cathode is lithium cobaltate (LiCoO{sub 2})-Solid solutions of LiCoO{sub 2} in LiFeO{sub 2} show promise for long-lived cathode materials. We have found that small additions of LiCoO{sub 2} to LiFeO{sub 2} markedly decrease the resistivity of the cathode material. Cells containing the LiCoO{sub 2}-LiFeO{sub 2} cathodes have stable performance for more than 2100 h of operation and display lower cobalt migration.

  13. 1D nanostructured Na7V4(P2O7)4(PO4) as high-potential and superior-performance cathode material for sodium-ion batteries.

    PubMed

    Deng, Chao; Zhang, Sen

    2014-06-25

    Tailoring materials into nanostructure offers unprecedented opportunities in the utilization of their functional properties. High-purity Na7V4(P2O7)4(PO4) with 1D nanostructure is prepared as a cathode material for rechargeable Na-ion batteries. An efficient synthetic approach is developed by carefully controlling the crystal growth in the molten sodium phosphate. Based on the XRD, XPS, TG, and morphological characterization, a molten-salt assisted mechanism for nanoarchitecture formation is revealed. The prepared Na7V4(P2O7)4(PO4) nanorod has rectangle sides and preferential [001] growth orientation. GITT evaluation indicates that the sodium de/intercalation of Na7V4(P2O7)4(PO4) nanorod involves V(3+)/V(4+) redox reaction and Na5V(3.5+)4(P2O7)4(PO4) as intermediate phase, which results in two pairs of potential plateaus at the equilibrium potentials of 3.8713 V (V(3+)/V(3.5+)) and 3.8879 V (V(3.5+)/V(4+)), respectively. The unique nanoarchitecture of the phase-pure Na7V4(P2O7)4(PO4) facilitates its reversible sodium de/intercalation, which is beneficial to the high-rate capability and the cycling stability. The Na7V4(P2O7)4(PO4) cathode delivers 80% of the capacity (obtained at C/20) at the 10 C rate and 95% of the initial capacity after 200 cycles. Therefore, it is feasible to design and fabricate an advanced rechargeable sodium-ion battery by employment of 1D nanostructured Na7V4(P2O7)4(PO4) as the cathode material.

  14. Thermionic Cathode Project

    NASA Astrophysics Data System (ADS)

    Getty, W. D.; Herniter, M. E.

    1986-01-01

    A planar cathode, Pierce type electron gun with a design perveance of .0000032 (amps/volts to the 3/2 power) has been operated with a lanthanum hexaboride (LaB6) cathode. The cathode (useful diameter 1.9 cm) is heated by bombardment by electrons from a small tungsten filament. The bombardment heating system is stabilized by a feedback control circuit. The power required to heat the cathode is 315 W bombardment power and 200 W filament power. Heating power has been reduced by careful heat shielding and reduction of heat conduction losses. Significant additional reductions should be possible. The sintered LaB6 cathode disk is 2.5 cm in diameter, 3.2 mm thick, and has a density of 94%. No problems have been encountered with cracking of the disk. Cathode emission is insensitive to repeated exposure to air after allowing the cathode to fully cool. The measured perveance and anode transmission of the gun are 3.2x10(-6) and 94%, respectively. Current densities up to 6.5 A/sq cm have been reached with 5 micrometer pulses. Measurements were made at cathode temperatures of 1300 to 1600 C.

  15. Sulfur/graphitic hollow carbon sphere nano-composite as a cathode material for high-power lithium-sulfur battery.

    PubMed

    Shin, Eon Sung; Kim, Min-Seop; Cho, Won Il; Oh, Si Hyoung

    2013-08-03

    The intrinsic low conductivity of sulfur which leads to a low performance at a high current rate is one of the most limiting factors for the commercialization of lithium-sulfur battery. Here, we present an easy and convenient method to synthesize a mono-dispersed hollow carbon sphere with a thin graphitic wall which can be utilized as a support with a good electrical conductivity for the preparation of sulfur/carbon nano-composite cathode. The hollow carbon sphere was prepared from the pyrolysis of the homogenous mixture of the mono-dispersed spherical silica and Fe-phthalocyanine powder in elevated temperature. The composite cathode was manufactured by infiltrating sulfur melt into the inner side of the graphitic wall. The electrochemical cycling shows a capacity of 425 mAh g-1 at 3 C current rate which is more than five times larger than that for the sulfur/carbon black nano-composite prepared by simple ball milling.

  16. A lithium-sulfur cathode with high sulfur loading and high capacity per area: a binder-free carbon fiber cloth-sulfur material.

    PubMed

    Miao, Lixiao; Wang, Weikun; Yuan, Keguo; Yang, Yusheng; Wang, Anbang

    2014-11-11

    A sulfur cathode with high capacity per area (>7 mA h cm(-2)) and high sulfur loading (6.7 mg cm(-2)) was fabricated by synthesizing a carbon fiber cloth-sulfur composite via a simple method. It is worth noting that an ingenious method is adopted which can improve the performance of Li-S batteries by forming in situ polysulfide ions.

  17. Microscopical characterization of carbon materials derived from coal and petroleum and their interaction phenomena in making steel electrodes, anodes and cathode blocks for the Microscopy of Carbon Materials Working Group of the ICCP

    USGS Publications Warehouse

    Predeanu, G.; Panaitescu, C.; Bălănescu, M.; Bieg, G.; Borrego, A.G.; Diez, M. A.; Hackley, Paul C.; Kwiecińska, B.; Marques, M.; Mastalerz, Maria; Misz-Kennan, M.; Pusz, S.; Suarez-Ruiz, I.; Rodrigues, S.; Singh, A. K.; Varma, A. K.; Zdravkov, A.; Zivotić, D.

    2015-01-01

    This paper describes the evaluation of petrographic textures representing the structural organization of the organic matter derived from coal and petroleum and their interaction phenomena in the making of steel electrodes, anodes and cathode blocks.This work represents the results of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology between the years 2009 and 2013. The round robin exercises were run on photomicrograph samples. For textural characterization of carbon materials the existing ASTM classification system for metallurgical coke was applied.These round robin exercises involved 15 active participants from 12 laboratories who were asked to assess the coal and petroleum based carbons and to identify the morphological differences, as optical texture (isotropic/anisotropic), optical type (punctiform, mosaic, fibre, ribbon, domain), and size. Four sets of digital black and white microphotographs comprising 151 photos containing 372 fields of different types of organic matter were examined. Based on the unique ability of carbon to form a wide range of textures, the results showed an increased number of carbon occurrences which have crucial role in the chosen industrial applications.The statistical method used to evaluate the results was based on the “raw agreement indices”. It gave a new and original view on the analysts' opinion by not only counting the correct answers, but also all of the knowledge and experience of the participants. Comparative analyses of the average values of the level of overall agreement performed by each analyst in the exercises during 2009–2013 showed a great homogeneity in the results, the mean value being 90.36%, with a minimum value of 83% and a maximum value of 95%.

  18. Morphological Evolution of High-Voltage Spinel LiNi(0.5)Mn(1.5)O4 Cathode Materials for Lithium-Ion Batteries: The Critical Effects of Surface Orientations and Particle Size.

    PubMed

    Liu, Haidong; Wang, Jun; Zhang, Xiaofei; Zhou, Dong; Qi, Xin; Qiu, Bao; Fang, Jianhui; Kloepsch, Richard; Schumacher, Gerhard; Liu, Zhaoping; Li, Jie

    2016-02-01

    An evolution panorama of morphology and surface orientation of high-voltage spinel LiNi(0.5)Mn(1.5)O4 cathode materials synthesized by the combination of the microwave-assisted hydrothermal technique and a postcalcination process is presented. Nanoparticles, octahedral and truncated octahedral particles with different preferential growth of surface orientations are obtained. The structures of different materials are studied by X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption near edge spectroscopy (XANES), and transmission electron microscopy (TEM). The influence of various morphologies (including surface orientations and particle size) on kinetic parameters, such as electronic conductivity and Li(+) diffusion coefficients, are investigated as well. Moreover, electrochemical measurements indicate that the morphological differences result in divergent rate capabilities and cycling performances. They reveal that appropriate surface-tailoring can satisfy simultaneously the compatibility of power capability and long cycle life. The morphology design for optimizing Li(+) transport and interfacial stability is very important for high-voltage spinel material. Overall, the crystal chemistry, kinetics and electrochemical performance of the present study on various morphologies of LiNi(0.5)Mn(1.5)O4 spinel materials have implications for understanding the complex impacts of electrode interface and electrolyte and rational design of rechargeable electrode materials for lithium-ion batteries. The outstanding performance of our truncated octahedral LiNi(0.5)Mn(1.5)O4 materials makes them promising as cathode materials to develop long-life, high energy and high power lithium-ion batteries.

  19. Advanced rechargeable sodium batteries with novel cathodes

    NASA Technical Reports Server (NTRS)

    Di Stefano, S.; Ratnakumar, B. V.; Bankston, C. P.

    1990-01-01

    Various high energy density rechargeable batteries are being considered for future space applications. Of these, the sodium-sulfur battery is one of the leading candidates. The primary advantage is the high energy density (760 W h/kg theoretical). Energy densities in excess of 180 W h/kg have been realized in practical batteries. More recently, cathodes other than sulfur are being evaluated. Various new cathode materials are presently being evaluated for use in high energy density sodium batteries for advanced space applications. The approach is to carry out basic electrochemical studies of these materials in a sodium cell configuration in order to understand their fundamental behaviors. Thus far, the studies have focussed on alternative metal chlorides such as CuCl2 and organic cathode materials such as TCNE.

  20. Advanced rechargeable sodium batteries with novel cathodes

    NASA Technical Reports Server (NTRS)

    Distefano, S.; Ratnakumar, B. V.; Bankston, C. P.

    1989-01-01

    Various high energy density rechargeable batteries are being considered for future space applications. Of these, the sodium sulfur battery is one of the leading candidates. The primary advantage is the high energy density (760 Wh/kg theoretical). Energy densities in excess of 180 Wh/kg have been realized in practical batteries. More recently, cathodes other than sulfur are being evaluated. Researchers at JPL are evaluating various new cathode materials for use in high energy density sodium batteries for advanced space applications. The approach is to carry out basic electrochemical studies of these materials in a sodium cell configuration in order to understand their fundamental behaviors. Thus far studies have focused on alternate metal chlorides such as CuCl2 and organic cathode materials such as tetracyanoethylene (TCNE).