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Sample records for lithium electrode surface

  1. Surface protected lithium-metal-oxide electrodes

    DOEpatents

    Thackeray, Michael M.; Kang, Sun-Ho

    2016-04-05

    A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

  2. Chemical and morphological characteristics of lithium electrode surfaces

    NASA Technical Reports Server (NTRS)

    Yen, S. P. S.; Shen, D.; Vasquez, R. P.; Grunthaner, F. J.; Somoano, R. B.

    1981-01-01

    Lithium electrode surfaces were analyzed for chemical and morphological characteristics, using electron spectroscopy chemical analysis (ESCA) and scanning electron microscopy (SEM). Samples included lithium metal and lithium electrodes which were cycled in a 1.5 M lithium arsenic hexafluoride/two-methyl tetrahydrofuran electrolyte. Results show that the surface of the as-received lithium metal was already covered by a film composed of LiO2 and an Li2O/CO2 adduct with a thickness of approximately 100-200 A. No evidence of Ni3 was found. Upon exposure of the lithium electrode to a 1.5 M LiAsF6/2-Me-THF electrochemical environment, a second film was observed to form on the surface, consisting primarily of As, Si, and F, possibly in the form of lithium arsenic oxyfluorides or lithium fluorosilicates. It is suggested that the film formation may be attributed to salt degradation.

  3. Surface passivation of natural graphite electrode for lithium ion battery by chlorine gas.

    PubMed

    Suzuki, Satoshi; Mazej, Zoran; Zemva, Boris; Ohzawa, Yoshimi; Nakajima, Tsuyoshi

    2013-01-01

    Surface lattice defects would act as active sites for electrochemical reduction of propylene carbonate (PC) as a solvent for lithium ion battery. Effect of surface chlorination of natural graphite powder has been investigated to improve charge/discharge characteristics of natural graphite electrode in PC-containing electrolyte solution. Chlorination of natural graphite increases not only surface chlorine but also surface oxygen, both of which would contribute to the decrease in surface lattice defects. It has been found that surface-chlorinated natural graphite samples with surface chlorine concentrations of 0.5-2.3 at% effectively suppress the electrochemical decomposition of PC, highly reducing irreversible capacities, i.e. increasing first coulombic efficiencies by 20-30% in 1 mol L-1 LiClO4-EC/DEC/PC (1:1:1 vol.). In 1 mol L-1 LiPF6-EC/EMC/PC (1:1:1 vol.), the effect of surface chlorination is observed at a higher current density. This would be attributed to decrease in surface lattice defects of natural graphite powder by the formation of covalent C-Cl and C=O bonds. PMID:24169705

  4. Improving lithium-sulphur batteries through spatial control of sulphur species deposition on a hybrid electrode surface.

    PubMed

    Yao, Hongbin; Zheng, Guangyuan; Hsu, Po-Chun; Kong, Desheng; Cha, Judy J; Li, Weiyang; Seh, Zhi Wei; McDowell, Matthew T; Yan, Kai; Liang, Zheng; Narasimhan, Vijay Kris; Cui, Yi

    2014-01-01

    Lithium-sulphur batteries are attractive owing to their high theoretical energy density and reasonable kinetics. Despite the success of trapping soluble polysulphides in a matrix with high surface area, spatial control of solid-state sulphur and lithium sulphide species deposition as a critical aspect has not been demonstrated. Herein, we show a clear visual evidence that these solid species deposit preferentially onto tin-doped indium oxide instead of carbon during electrochemical charge/discharge of soluble polysuphides. To incorporate this concept of spatial control into more practical battery electrodes, we further prepare carbon nanofibers with tin-doped indium oxide nanoparticles decorating the surface as hybrid three-dimensional electrodes to maximize the number of deposition sites. With 12.5 μl of 5 M Li2S8 as the catholyte and a rate of C/5, we can reach the theoretical limit of Li2S8 capacity ~\

  5. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Kim, Jeom-Soo; Johnson, Christopher S.

    2008-01-01

    An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li.sub.(2+2x)/(2+x)M'.sub.2x/(2+x)M.sub.(2-2x)/(2+x)O.sub.2-.delta., in which 0.ltoreq.x<1 and .delta. is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

  6. Conductive lithium storage electrode

    DOEpatents

    Chiang, Yet-Ming; Chung, Sung-Yoon; Bloking, Jason T.; Andersson, Anna M.

    2008-03-18

    A compound comprising a composition A.sub.x(M'.sub.1-aM''.sub.a).sub.y(XD.sub.4).sub.z, A.sub.x(M'.sub.1-aM''.sub.a).sub.y(DXD.sub.4).sub.z, or A.sub.x(M'.sub.1-aM''.sub.a).sub.y(X.sub.2D.sub.7).sub.z, and have values such that x, plus y(1-a) times a formal valence or valences of M', plus ya times a formal valence or valence of M'', is equal to z times a formal valence of the XD.sub.4, X.sub.2D.sub.7, or DXD.sub.4 group; or a compound comprising a composition (A.sub.1-aM''.sub.a).sub.xM'.sub.y(XD.sub.4).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(DXD.sub.4).sub.z(A.sub.1-aM''.sub.a).s- ub.xM'.sub.y(X.sub.2D.sub.7).sub.z and have values such that (1-a).sub.x plus the quantity ax times the formal valence or valences of M'' plus y times the formal valence or valences of M' is equal to z times the formal valence of the XD.sub.4, X.sub.2D.sub.7 or DXD.sub.4 group. In the compound, A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M'' any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001lithium phosphate that can intercalate lithium or hydrogen. The compound can be used in an electrochemical device including electrodes and storage batteries and can have a gravimetric capacity of at least about 80 mAh/g while being charged/discharged at greater than about C rate of the compound.

  7. Conductive lithium storage electrode

    DOEpatents

    Chiang, Yet-Ming; Chung, Sung-Yoon; Bloking, Jason T.; Andersson, Anna M.

    2012-04-03

    A compound comprising a composition A.sub.x(M'.sub.1-aM''.sub.a).sub.y(XD.sub.4).sub.z, A.sub.x(M'.sub.1-aM''.sub.a).sub.y(DXD.sub.4).sub.z, or A.sub.x(M'.sub.1-aM''.sub.a).sub.y(X.sub.2D.sub.7).sub.z, and have values such that x, plus y(1-a) times a formal valence or valences of M', plus ya times a formal valence or valence of M'', is equal to z times a formal valence of the XD.sub.4, X.sub.2D.sub.7, or DXD.sub.4 group; or a compound comprising a composition (A.sub.1-aM''.sub.a).sub.xM'.sub.y(XD.sub.4).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(DXD.sub.4).sub.z (A.sub.1-aM''.sub.a).sub.xM'.sub.y(X.sub.2D.sub.7).sub.z and have values such that (1-a).sub.x plus the quantity ax times the formal valence or valences of M'' plus y times the formal valence or valences of M' is equal to z times the formal valence of the XD.sub.4, X.sub.2D.sub.7 or DXD.sub.4 group. In the compound, A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M'' any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001lithium phosphate that can intercalate lithium or hydrogen. The compound can be used in an electrochemical device including electrodes and storage batteries and can have a gravimetric capacity of at least about 80 mAh/g while being charged/discharged at greater than about C rate of the compound.

  8. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kang, Sun-Ho

    2010-06-08

    An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which 0lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. The xLi.sub.2-yH.sub.y.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 material is prepared by preconditioning a precursor lithium metal oxide (i.e., xLi.sub.2M'O.sub.3.(1-x)LiMO.sub.2) with a proton-containing medium with a pH<7.0 containing an inorganic acid. Methods of preparing the electrodes are disclosed, as are electrochemical cells and batteries containing the electrodes.

  9. Electrode for a lithium cell

    DOEpatents

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2008-10-14

    This invention relates to a positive electrode for an electrochemical cell or battery, and to an electrochemical cell or battery; the invention relates more specifically to a positive electrode for a non-aqueous lithium cell or battery when the electrode is used therein. The positive electrode includes a composite metal oxide containing AgV.sub.3O.sub.8 as one component and one or more other components consisting of LiV.sub.3O.sub.8, Ag.sub.2V.sub.4O.sub.11, MnO.sub.2, CF.sub.x, AgF or Ag.sub.2O to increase the energy density of the cell, optionally in the presence of silver powder and/or silver foil to assist in current collection at the electrode and to improve the power capability of the cell or battery.

  10. Role of surface oxides in the formation of solid-electrolyte interphases at silicon electrodes for lithium-ion batteries.

    PubMed

    Schroder, Kjell W; Dylla, Anthony G; Harris, Stephen J; Webb, Lauren J; Stevenson, Keith J

    2014-12-10

    Nonaqueous solvents in modern battery technologies undergo electroreduction at negative electrodes, leading to the formation of a solid-electrolyte interphase (SEI). The mechanisms and reactions leading to a stable SEI on silicon electrodes in lithium-ion batteries are still poorly understood. This lack of understanding inhibits the rational design of electrolyte additives, active material coatings, and the prediction of Li-ion battery life in general. We prepared SEI with a common nonaqueous solvent (LiPF6 in PC and in EC/DEC 1:1 by wt %) on silicon oxide and etched silicon (001) surfaces in various states of lithiation to understand the role of surface chemistry on the SEI formation mechanism and SEI structure. Anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films, allowing for more accurate characterization of SEI chemical stratification and composition by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling. Additionally, multivariate statistical methods were used to better understand TOF-SIMS depth profiling studies. We conclude that the absence of native-oxide layer on silicon has a significant impact on the formation, composition, structure, and thickness of the SEI. PMID:25402271

  11. Lithium intercalation in porous carbon electrodes

    SciTech Connect

    Tran, T.D.; Feikert, J.; Pekala, R.W.

    1995-04-01

    Carbons derived from the phase separation of polyacrylonitrile/solvent mixtures were investigated as lithium intercalation anodes for rechargeable lithium-ion batteries. The carbon electrodes have a bulk density of 0.35-0.5 g/cm{sup 3}, relatively low surface areas (< 10 m{sup 2}/g), and micron-size cells. Pyrolysis temperature influences the reversible lithium intercalation and the irreversible capacity (associated with the formation of the passivating layer). Carbon electrodes pyrolyzed at 600{degrees}C have first-cycle capacity as high as 550 mAh/g as well as large irreversible capacity, 440 mAh/g. Electrodes prepared at 1050{degrees}C have reversible capacities around 270 mAh/g with relatively lower capacity losses (120 mAh/g). Doping the organic precursors with phosphoric acid, prior to pyrolysis at 1050{degrees}C, leads to carbon electrodes with reversible capacities as high as 450 mAh/g. The capacity of doped carbon increased with increasing phosphorus concentration in the samples. The doped carbon anodes exhibited good cycleability and excellent coulombic efficiency. The electrochemical performance is related to morphology, chemical composition, and local structural order.

  12. Lithium-aluminum-iron electrode composition

    DOEpatents

    Kaun, Thomas D.

    1979-01-01

    A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

  13. Conductive lithium storage electrode

    DOEpatents

    Chiang, Yet-Ming; Chung, Sung-Yoon; Bloking, Jason T; Andersson, Anna M

    2014-10-07

    A compound comprising a composition A.sub.x(M'.sub.1-aM''.sub.a).sub.y(XD.sub.4).sub.z, A.sub.x(M'.sub.1-aM''.sub.a).sub.y(DXD.sub.4).sub.z, or A.sub.x(M'.sub.1-aM''.sub.a).sub.y(X.sub.2D.sub.7).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(XD.sub.4).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(DXD.sub.4).sub.z, or (A.sub.1-aM''.sub.a).sub.xM'.sub.y(X.sub.2D.sub.7).sub.z. In the compound, A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M'' any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001electrodes and storage batteries.

  14. A simple and novel Si surface modification on LiFePO4@C electrode and its suppression of degradation of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Wenyu; Zhuang, Zhenyuan; Chen, Xiang; Zou, Mingzhong; Zhao, Guiying; Feng, Qian; Li, Jiaxin; Lin, Yingbin; Huang, Zhigao

    2015-12-01

    A simple and novel surface modification device of the electrodes based on the ultrasonic spray technique was set up, which is considered to have the enormous prospect of industrial application due to its simpleness and high efficiency. Then, the nano-sized Si nanoparticles were deposited uniformly on the LiFePO4@C electrodes. In comparison with pristine LiFePO4@C electrode, the surface modification of the nano-sized Si with crystalline Si core and amorphous Si shell on the electrode surface exhibits less coarsening degree, higher rate capability, better cyclicity at high charge/discharge rate, especially at elevated temperature. Moreover, Raman spectra of LiFePO4@C, LiFePO4@C/Si electrodes before cycles and after 100 cycles at 1 C and 60 °C were measured. It is found that the FePO4 and α-Fe2O3 phases exist in LiFePO4@C after 100 cycles. On the contrary, there hardly exists the FePO4 and α-Fe2O3 phases, which means that the nano Si surface modification suppresses the degradation of lithium ion batteries. At last, the schematic and phenomenological resistance models of LiFePO4@C electrode modified by the nano-sized silicon particles have been suggested, which is responsible for the enhancement of the electrochemical performances after nano-sized Si surface modification.

  15. Lithium metal doped electrodes for lithium-ion rechargeable chemistry

    DOEpatents

    Liu, Gao; Battaglia, Vince; Wang, Lei

    2016-09-13

    An embodiment of the invention combines the superior performance of a polyvinylidene difluoride (PVDF) or polyethyleneoxide (POE) binder, the strong binding force of a styrene-butadiene (SBR) binder, and a source of lithium ions in the form of solid lithium metal powder (SLMP) to form an electrode system that has improved performance as compared to PVDF/SBR binder based electrodes. This invention will provide a new way to achieve improved results at a much reduced cost.

  16. Lithium-aluminum-magnesium electrode composition

    DOEpatents

    Melendres, Carlos A.; Siegel, Stanley

    1978-01-01

    A negative electrode composition is presented for use in a secondary, high-temperature electrochemical cell. The cell also includes a molten salt electrolyte of alkali metal halides or alkaline earth metal halides and a positive electrode including a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent and a magnesium-aluminum alloy as a structural matrix. Various binary and ternary intermetallic phases of lithium, magnesium, and aluminum are formed but the electrode composition in both its charged and discharged state remains substantially free of the alpha lithium-aluminum phase and exhibits good structural integrity.

  17. Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

    NASA Technical Reports Server (NTRS)

    Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor); Attia, Alan I. (Inventor); Halpert, Gerald (Inventor)

    1995-01-01

    The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

  18. Ternary compound electrode for lithium cells

    DOEpatents

    Raistrick, Ian D.; Godshall, Ned A.; Huggins, Robert A.

    1982-01-01

    Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and of light weight. One type of lithium-based cell utilizes a molten salt electrolyte and normally is operated in the temperature range of about 350.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems. The present invention provides an electrochemical cell in which lithium is the electroactive species. The cell has a positive electrode which includes a ternary compound generally represented as Li-M-O, wherein M is a transition metal. Corrosion of the inventive cell is considerably reduced.

  19. Ternary compound electrode for lithium cells

    DOEpatents

    Raistrick, I.D.; Godshall, N.A.; Huggins, R.A.

    1980-07-30

    Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and of light weight. One type of lithium-based cell utilizes a molten salt electrolyte and normally is operated in the temperature range of about 350 to 500/sup 0/C. Such high temperature operation accelerates corrosion problems. The present invention provides an electrochemical cell in which lithium is the electroactive species. The cell has a positive electrode which includes a ternary compound generally represented as Li-M-O, wherein M is a transition metal. Corrosion of the inventive cell is considerably reduced.

  20. Cells containing solvated electron lithium negative electrodes

    NASA Astrophysics Data System (ADS)

    Uribe, Francisco A.; Semkow, Krystyna W.; Sammells, Anthony F.

    1989-12-01

    This paper presents results obtained on cells based on solvated electron lithium negative electrodes, which may have application in high-energy-density secondary or reserve battery systems. The approach uses Li initially dissolved in liquid ammonia to give a solvated electron lithium/ammonia solution. This liquid negative active material is protected from direct contact with the liquid nonaqueous electrolyte in the positive electrode compartment by a lithium-intercalated electronically conducting ceramic membrane possessing Li(x)WoO2 composition with x values between 0.1 and 1.0. Depending upon initial lithium activity in the negative electrode compartments, the experimental cell was found to possess an initial open-circuit potential between 2.1 and 2.5 V.

  1. Layered electrodes for lithium cells and batteries

    DOEpatents

    Johnson; Christopher S. , Thackeray; Michael M. , Vaughey; John T. , Kahaian; Arthur J. , Kim; Jeom-Soo

    2008-04-15

    Lithium metal oxide compounds of nominal formula Li.sub.2MO.sub.2, in which M represents two or more positively charged metal ions, selected predominantly and preferably from the first row of transition metals are disclosed herein. The Li.sub.2MO.sub.2 compounds have a layered-type structure, which can be used as positive electrodes for lithium electrochemical cells, or as a precursor for the in-situ electrochemical fabrication of LiMO.sub.2 electrodes. The Li.sub.2MO.sub.2 compounds of the invention may have additional functions in lithium cells, for example, as end-of-discharge indicators, or as negative electrodes for lithium cells.

  2. Long life lithium batteries with stabilized electrodes

    DOEpatents

    Amine, Khalil; Liu, Jun; Vissers, Donald R.; Lu, Wenquan

    2009-03-24

    The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

  3. Lithium electronic environments in rechargeable battery electrodes

    NASA Astrophysics Data System (ADS)

    Hightower, Adrian

    This work investigates the electronic environments of lithium in the electrodes of rechargeable batteries. The use of electron energy-loss spectroscopy (EELS) in conjunction with transmission electron microscopy (TEM) is a novel approach, which when coupled with conventional electrochemical experiments, yield a thorough picture of the electrode interior. Relatively few EELS experiments have been preformed on lithium compounds owing to their reactivity. Experimental techniques were established to minimize sample contamination and control electron beam damage to studied compounds. Lithium hydroxide was found to be the most common product of beam damaged lithium alloys. Under an intense electron beam, halogen atoms desorbed by radiolysis in lithium halides. EELS spectra from a number of standard lithium compounds were obtained in order to identify the variety of spectra encountered in lithium rechargeable battery electrodes. Lithium alloys all displayed characteristically broad Li K-edge spectra, consistent with transitions to continuum states. Transitions to bound states were observed in the Li K and oxygen K-edge spectra of lithium oxides. Lithium halides were distinguished by their systematic chemical shift proportional to the anion electronegativity. Good agreement was found with measured lithium halide spectra and electron structure calculations using a self-consistant multiscattering code. The specific electrode environments of LiC6, LiCoO2, and Li-SnO were investigated. Contrary to published XPS predictions, lithium in intercalated graphite was determined to be in more metallic than ionic. We present the first experimental evidence of charge compensation by oxygen ions in deintercalated LiCoO2. Mossbauer studies on cycled Li-SnO reveal severely defective structures on an atomic scale. Metal hydride systems are presented in the appendices of this thesis. The mechanical alloying of immiscible Fe and Mg powders resulted in single-phase bcc alloys of less than 20

  4. Lithium Manganese Silicate Positive Electrode Material

    NASA Astrophysics Data System (ADS)

    Yang, Qiong

    As the fast development of the electronic portable devices and drastic fading of fossil energy sources. The need for portable secondary energy sources is increasingly urgent. As a result, lithium ion batteries are being investigated intensely to meet the performance requirements. Among various electrode materials, the most expensive and capacity limiting component is the positive materials. Based on this, researches have been mostly focused on the development of novel cathode materials with high capacity and energy density and the lithium transition metal orthosilicates have been identified as possible high performance cathodes. Here in, we report the synthesis of a kind of lithium transition metal orthosilicates electrode lithium manganese silicate. Lithium manganese silicate has the advantage of high theoretical capacity, low cost raw material and safety. In this thesis, lithium manganese silicate are prepared using different silicon sources. The structure of silicon sources preferred are examined. Nonionic block copolymers surfactant, P123, is tried as carbon source and mophology directing agent. Lithium manganese silicate's performances are improved by adding P123.

  5. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

    Johnson, Christopher S.; Kang, Sun-Ho; Thackeray, Michael M.

    2009-12-22

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0.5electrode and 0.ltoreq.y<1 in which the Li.sub.2MnO.sub.3 and LiMn.sub.2-yM.sub.yO.sub.4 components have layered and spinel-type structures, respectively, and in which M is one or more metal cations. The electrode is activated by removing lithia, or lithium and lithia, from the precursor. A cell and battery are also disclosed incorporating the disclosed positive electrode.

  6. Method of preparing a negative electrode including lithium alloy for use within a secondary electrochemical cell

    DOEpatents

    Tomczuk, Zygmunt; Olszanski, Theodore W.; Battles, James E.

    1977-03-08

    A negative electrode that includes a lithium alloy as active material is prepared by briefly submerging a porous, electrically conductive substrate within a melt of the alloy. Prior to solidification, excess melt can be removed by vibrating or otherwise manipulating the filled substrate to expose interstitial surfaces. Electrodes of such as solid lithium-aluminum filled within a substrate of metal foam are provided.

  7. Silver manganese oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2006-05-09

    This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

  8. Stabilization of insertion electrodes for lithium batteries.

    SciTech Connect

    Thackeray, M. M.

    1998-09-03

    This paper discusses the techniques that are being employed to stabilize LiMn{sub 2}O{sub 4} spinel and composite Li{sub x}MnO{sub 2} positive electrodes. The critical role that spinel domains play in stabilizing these electrodes for operation at both 4 V and 3 V is highlighted. The concept of using an intermetallic electrode MM{prime} where M is an active alloying element and M{prime} is an inactive element (or elements) is proposed as an alternative negative electrode (to carbon) for lithium-ion cells. An analogy to metal oxide insertion electrodes, such as MnO{sub 2}, in which Mn is the electrochemically active ion and O is the inactive ion, is made. Performance data are given for the copper-tin electrode system, which includes the intermetallic phases eta-Cu{sub 6}Sn{sub 5} and Li{sub 2}CuSn.

  9. High-capacity phase formation by surface modification of Li3PO4 on nanosized Li2RuO3 electrode for lithium batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Yueming; Taminato, Sou; Xu, Youlong; Suzuki, Kota; Kim, KyungSu; Hirayama, Masaaki; Kanno, Ryoji

    2012-06-01

    Effects of modifying the surface of lithium excess layered rock-salt type electrodes by Li3PO4 is investigated using epitaxial Li2RuO3 model electrodes. A 3.6-nm-thick amorphous Li3PO4 layer is deposited on a 25.5-nm-thick Li2RuO3 film by pulsed laser deposition. X-ray absorption near edge structure reveals that the modified Li2RuO3 surface had different electronic states of Ru from the unmodified Li2RuO3 surface, indicating that Li3PO4 deposition changes the structure of the Li2RuO3 surface. Li3PO4-modified Li2RuO3 has a much higher first discharge capacity (296 mAh g-1) between 2.8 and 4.2 V than unmodified Li2RuO3 (190 mAh g-1). The modified and unmodified Li2RuO3 have irreversible capacities in the first charge/discharge process of 22 and 148 mAh g-1, respectively. The surface modification induced by Li3PO4 deposition enhances the structural stability of the Li2RuO3 surface during the initial charging process.

  10. Spinel electrodes for rechargeable lithium batteries.

    SciTech Connect

    Thackeray, M. M.

    1999-11-10

    This paper gives a historical account of the development of spinel electrodes for rechargeable lithium batteries. Research in the late 1970's and early 1980's on high-temperature . Li/Fe{sub 3}O{sub 4} cells led to the evaluation of lithium spinels Li[B{sub 2}]X{sub 4} at room temperature (B = metal cation). This work highlighted the importance of the [B{sub 2}]X{sub 4}spinel framework as a host electrode structure and the ability to tailor the cell voltage by selection of different B cations. Examples of lithium-ion cells that operate with spinel anode/spinel cathode couples are provided. Particular attention is paid to spinels within the solid solution system Li{sub 1+x}Mn{sub 2-x}O{sub 4} (0 {le} x {le} 0.33).

  11. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

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

    2007-12-04

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0electrode is activated by removing lithia, or lithium and lithia, from the precursor. A cell and battery are also disclosed incorporating the disclosed positive electrode.

  12. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

    2006-11-14

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0

  13. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

    2004-01-13

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2 M'O.sub.3 in which 0

  14. Polymer nanofiber-guided uniform lithium deposition for battery electrodes.

    PubMed

    Liang, Zheng; Zheng, Guangyuan; Liu, Chong; Liu, Nian; Li, Weiyang; Yan, Kai; Yao, Hongbin; Hsu, Po-Chun; Chu, Steven; Cui, Yi

    2015-05-13

    Lithium metal is one of the most promising candidates as an anode material for next-generation energy storage systems due to its highest specific capacity (3860 mAh/g) and lowest redox potential of all. The uncontrolled lithium dendrite growth that causes a poor cycling performance and serious safety hazards, however, presents a significant challenge for the realization of lithium metal-based batteries. Here, we demonstrate a novel electrode design by placing a three-dimensional (3D) oxidized polyacrylonitrile nanofiber network on top of the current collector. The polymer fiber with polar surface functional groups could guide the lithium ions to form uniform lithium metal deposits confined on the polymer fiber surface and in the 3D polymer layer. We showed stable cycling of lithium metal anode with an average Coulombic efficiency of 97.4% over 120 cycles in ether-based electrolyte at a current density of 3 mA/cm(2) for a total of 1 mAh/cm(2) of lithium. PMID:25822282

  15. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil

    2008-12-23

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0

  16. Lithium Metal Oxide Electrodes For Lithium Cells And Batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

    2004-01-20

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2 M'O.sub.3 in which 0

  17. Vanadium diaphragm electrode serves as hydrogen diffuser in lithium hydride cell

    NASA Technical Reports Server (NTRS)

    Crouthamel, C. E.; Heinrich, R. R.; Johnson, C. E.

    1967-01-01

    Lithium hydride cell uses vanadium diaphragm electrode as a hydrogen diffuser. Vanadium is high in hydrogen gas solubility and permeability, is least sensitive to adverse surface effects, maintains good mechanical strength in hydrogen atmospheres, and appears to be compatible with all alkali-halide electrolytes and lithium metals.

  18. Lithium battery electrodes with ultra-thin alumina coatings

    SciTech Connect

    Se-Hee, Lee; George, Steven M.; Cavanagh, Andrew S.; Yoon Seok, Jung; Dillon, Anne C.

    2015-11-24

    Electrodes for lithium batteries are coated via an atomic layer deposition process. The coatings can be applied to the assembled electrodes, or in some cases to particles of electrode material prior to assembling the particles into an electrode. The coatings can be as thin as 2 .ANG.ngstroms thick. The coating provides for a stable electrode. Batteries containing the electrodes tend to exhibit high cycling capacities.

  19. Method of preparing a negative electrode including lithium alloy for use within a secondary electrochemical cell

    DOEpatents

    Tomczuk, Z.; Olszanski, W.; Battles, J.E.

    1975-12-09

    A negative electrode that includes a lithium alloy as active material is prepared by briefly submerging a porous, electrically conductive substrate within a melt of the alloy. Prior to solidification, excess melt can be removed by vibrating or otherwise manipulating the filled substrate to expose interstitial surfaces. Electrodes of such a solid lithium--aluminum filled within a substrate of metal foam are provided. 1 figure, 1 table.

  20. Methods for making lithium vanadium oxide electrode materials

    DOEpatents

    Schutts, Scott M.; Kinney, Robert J.

    2000-01-01

    A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

  1. ac conductance of surface layer in lithium tetraborate single crystals

    NASA Astrophysics Data System (ADS)

    Kim, Chung-Sik; Park, Jong-Ho; Moon, Byung Kee; Seo, Hyo-Jin; Choi, Byung-Chun; Hwang, Yoon-Hwae; Kim, Hyung Kook; Kim, Jung Nam

    2003-12-01

    ac conductance for the electrode effect in Li2B4O7 single crystal was investigated by use of a coplanar electrode applied on the surface of a (001) plate. A coplanar electrode in this material more clearly shows conduction of the electrode effect than a conventional parallel planar electrode. The electrode effect in ac conductance is likely to be controlled by the surface layer, which is a poorly conductive depletion layer possibly filled with vacancies of lithium ions. We found that the surface layer is not locally distributed near the electrodes, but, rather, on the broad area of the surface (001) plane of the material. So we conclude that the electrode effect in ac conduction of Li2B4O7 single crystal is mainly due to the poor conductive surface layer distributed over the whole surface of the (001) plane and is not a secondary phase formed by reaction with the electrode material.

  2. Lithium aluminum/iron sulfide battery having lithium aluminum and silicon as negative electrode

    DOEpatents

    Gilbert, Marian; Kaun, Thomas D.

    1984-01-01

    A method of making a negative electrode, the electrode made thereby and a secondary electrochemical cell using the electrode. Silicon powder is mixed with powdered electroactive material, such as the lithium-aluminum eutectic, to provide an improved electrode and cell.

  3. Surface-layer formation by reductive decomposition of LiPF6 at relatively high potentials on negative electrodes in lithium ion batteries and its suppression

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Tomoya; Shimada, Koki; Ichitsubo, Tetsu; Yagi, Shunsuke; Matsubara, Eiichiro

    2014-12-01

    In using a LiPF6/ethylene carbonate-dimethyl carbonate electrolyte for lithium ion batteries (LIBs), a certain reductive reaction is known to occur at a relatively high potential (ca. 2.6 V vs. Li+/Li) on Sn electrode, but its details are still unknown. By means of in-situ X-ray reflectometry, X-ray photoelectron spectroscopy, scanning electron microscopy observations and electrochemical measurements (by using mainly Sn electrode, and additionally Pt, graphite electrodes), we have found out that this reduction eventually forms an inactive passivation-layer consisting mainly of insulative LiF ascribed to the reductive decomposition of LiPF6, which significantly affects the battery cyclability. In contrast, a solid-electrolyte interphase (SEI) is formed by the reductive reaction of the solvent at ca. 1.5 V vs. Li+/Li, which is lower than the reduction potential of LiPF6. However, we have found that the formation of SEI preempts that of the passivation layer when holding the electrode at a potential lower than 1.5 V vs. Li+/Li. Consequently, the cyclability is improved by suppressing the formation of the inactive passivation layer. Such a pretreatment would be quite effective on improvement of the battery cyclability, especially for a relatively noble electrode whose oxidation potential is between 1.5 V and 2.6 V vs. Li+/Li.

  4. Multi-component intermetallic electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M; Trahey, Lynn; Vaughey, John T

    2015-03-10

    Multi-component intermetallic negative electrodes prepared by electrochemical deposition for non-aqueous lithium cells and batteries are disclosed. More specifically, the invention relates to composite intermetallic electrodes comprising two or more compounds containing metallic or metaloid elements, at least one element of which can react with lithium to form binary, ternary, quaternary or higher order compounds, these compounds being in combination with one or more other metals that are essentially inactive toward lithium and act predominantly, but not necessarily exclusively, to the electronic conductivity of, and as current collection agent for, the electrode. The invention relates more specifically to negative electrode materials that provide an operating potential between 0.05 and 2.0 V vs. metallic lithium.

  5. AC impedance electrochemical modeling of lithium-ion positive electrodes.

    SciTech Connect

    Dees, D.; Gunen, E.; Abraham, D.; Jansen, A.; Prakash, J.; Chemical Engineering; IIT

    2004-01-01

    Under Department of Energy's Advanced Technology Development Program,various analytical diagnostic studies are being carried out to examine the lithium-ion battery technology for hybrid electric vehicle applications, and a series of electrochemical studies are being conducted to examine the performance of these batteries. An electrochemical model was developed to associate changes that were observed in the post-test analytical diagnostic studies with the electrochemical performance loss during testing of lithium ion batteries. While both electrodes in the lithium-ion cell have been studied using a similar electrochemical model, the discussion here is limited to modeling of the positive electrode. The positive electrode under study has a composite structure made of a layered nickel oxide (LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}) active material, a carbon black and graphite additive for distributing current, and a PVDF binder all on an aluminum current collector. The electrolyte is 1.2M LiPF{sub 6} dissolved in a mixture of EC and EMC and a Celgard micro-porous membrane is used as the separator. Planar test cells (positive/separator/negative) were constructed with a special fixture and two separator membranes that allowed the placement of a micro-reference electrode between the separator membranes [1]. Electrochemical studies including AC impedance spectroscopy were then conducted on the individual electrodes to examine the performance and ageing effects in the cell. The model was developed by following the work of Professor Newman at Berkeley [2]. The solid electrolyte interface (SEI) region, based on post-test analytical results, was assumed to be a film on the oxide and an oxide layer at the surface of the oxide. A double layer capacity was added in parallel with the Butler-Volmer kinetic expression. The pertinent reaction, thermodynamic, and transport equations were linearized for a small sinusoidal perturbation [3]. The resulting system of differential

  6. Protective coating on positive lithium-metal-oxide electrodes for lithium batteries

    DOEpatents

    Johnson, Christopher S.; Thackeray, Michael M.; Kahaian, Arthur J.

    2006-05-23

    A positive electrode for a non-aqueous lithium cell comprising a LiMn2-xMxO4 spinel structure in which M is one or more metal cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0.ltoreq.x.ltoreq.0.15, having one or more lithium spine oxide LiM'2O4 or lithiated spinel oxide Li1+yM'2O4 compounds on the surface thereof in which M' are cobalt cations and in which 0.ltoreq.y.ltoreq.1.

  7. Application of Carbon Nanomaterials in Lithium-Ion Battery Electrodes

    NASA Astrophysics Data System (ADS)

    Jaber-Ansari, Laila

    Carbon nanomaterials such as single-walled carbon nanotubes (SWCNTs) and graphene have emerged as leading additives for high capacity nanocomposite lithium ion battery electrodes due to their ability to improve electrode conductivity, current collection efficiency, and charge/discharge rate for high power applications. In this work, the these nanomaterials have been developed and their properties have been fine-tuned to help solve fundamental issues in conventional lithium ion battery electrodes. Towards this end, the application of SWCNTs in lithium-ion anodes has been studied. As-grown SWCNTs possess a distribution of physical and electronic structures, and it is of high interest to determine which subpopulations of SWCNTs possess the highest lithiation capacity and to develop processing methods that can enhance the lithiation capacity of underperforming SWCNT species. Towards this end, SWCNT electronic type purity is controlled via density gradient ultracentrifugation, enabling a systematic study of the lithiation of SWCNTs as a function of metal versus semiconducting content. Experimentally, vacuum filtered freestanding films of metallic SWCNTs are found to accommodate lithium with an order of magnitude higher capacity than their semiconducting counterparts. In contrast, SWCNT film densification leads to the enhancement of the lithiation capacity of semiconducting SWCNTs to levels comparable to metallic SWCNTs, which is corroborated by theoretical calculations. To understand the interaction of the graphene with lithium ions and electrolyte species during electrochemical we use Raman spectroscopy in a model system of monolayer graphene transferred on a Si(111) substrate and density functional theory (DFT) to investigate defect formation as a function of lithiation. This model system enables the early stages of defect formation to be probed in a manner previously not possible with commonly-used reduced graphene oxide or multilayer graphene substrates. Using ex

  8. Long life lithium batteries with stabilized electrodes

    DOEpatents

    Amine, Khalil; Liu, Jun; Vissers, Donald R; Lu, Wenquan

    2015-04-21

    The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In certain electrolytes, the alkali metal salt is a bis(chelato)borate and the additives include substituted or unsubstituted linear, branched or cyclic hydrocarbons comprising at least one oxygen atom and at least one aryl, alkenyl or alkynyl group. In other electrolytes, the additives include a substituted aryl compound or a substituted or unsubstituted heteroaryl compound wherein the additive comprises at least one oxygen atom. There are also provided methods of making the electrolytes and batteries employing the electrolytes. The invention also provides for electrode materials. Cathodes of the present invention may be further stabilized by surface coating the particles of the spinel or olivine with a material that can neutralize acid or otherwise lessen or prevent leaching of the manganese or iron ions. In some embodiments the coating is polymeric and in other embodiments the coating is a metal oxide such as ZrO.sub.2, TiO.sub.2, ZnO, WO.sub.3, Al.sub.2O.sub.3, MgO, SiO.sub.2, SnO.sub.2 AlPO.sub.4, Al(OH).sub.3, a mixture of any two or more thereof.

  9. Electronically conductive polymer binder for lithium-ion battery electrode

    SciTech Connect

    Liu, Gao; Xun, Shidi; Battaglia, Vincent S; Zheng, Honghe

    2014-10-07

    A family of carboxylic acid group containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

  10. Electrode materials and lithium battery systems

    DOEpatents

    Amine, Khalil; Belharouak, Ilias; Liu, Jun

    2011-06-28

    A material comprising a lithium titanate comprising a plurality of primary particles and secondary particles, wherein the average primary particle size is about 1 nm to about 500 nm and the average secondary particle size is about 1 .mu.m to about 4 .mu.m. In some embodiments the lithium titanate is carbon-coated. Also provided are methods of preparing lithium titanates, and devices using such materials.

  11. Application of Carbon Nanomaterials in Lithium-Ion Battery Electrodes

    NASA Astrophysics Data System (ADS)

    Jaber-Ansari, Laila

    approximately three times the capacity with significantly superior cycling stability and power. X-ray photoelectron spectroscopy (XPS) depth profiling provides evidence that the graphene coating inhibits manganese depletion from the LMO surface. Furthermore, cross-section transmission electron microscopy (TEM) demonstrates that a stable solid electrolyte interphase (SEI) layer is formed on graphene, which screens the LMO from direct contact with the electrolyte, thereby prolonging the electrode life. Density functional theory (DFT) calculations support the hypothesis of graphene as a diffusion barrier: Defected graphene acts as a barrier for manganese diffusion while allowing the transport of lithium. However, DFT calculations also suggest that the role of graphene goes beyond a physical barrier. The reactive edge of graphene can chemically interact with Mn3+ at the electrode surface, promotes an oxidation state change (Mn3+→Mn4+) and suppresses dissolution and the Jahn-Teller distortion associated with Mn 3.

  12. Electrochemical and spectroscopic studies of carbon electrodes in lithium battery electrolyte systems

    NASA Astrophysics Data System (ADS)

    Chusid, O.; Ein Ely, E.; Aurbach, D.; Babai, M.; Carmeli, Y.

    1993-03-01

    In this work we studied several parameters that influence the intercalation of lithium ions into carbons (e.g. carbon type, binder and solution composition). The carbons investigated included carbon blacks (e.g. acetylene black, Ketjen black), graphite and carbon fibers. The solvents used in this study include methyl formate, propylene and ethylene carbonate, ethers (e.g. tetrahydrofuran) and their mixtures. The salts included LiClO 4, LiAsF 6 and LiBF 4. CO 2 was tested as an additive. The electrochemical behavior of the electrodes in solutions was followed by chronopotentiometry in galvanostatic charge/discharge cycling and their surface chemistry in solutions was investigated using surface sensitive Fourier-transform infrared spectroscopy (FT-IR) in transmittance, attenuated total reflectance and diffuse reflectance modes. It was found that the solvents and salts are reduced on the carbon electrodes at low potentials to form surface films. In general, their surface chemistry is quite similar to that of lithium or noble metal electrodes at low potential (in the same solutions). The electrochemical behavior of the carbon electrodes in terms of degree of intercalation and its reversibility is strongly affected by their surface chemistry. Reversible intercalation was obtained with graphite in methyl formate solutions containing CO 2. Some degree of reversible intercalation was also obtained with graphite in ethers. The presence of propylene carbonate in solution is detrimental for lithium intercalation in graphite. Reversible lithium-carbon intercalation was also obtained with acetylene black and carbonized polyacrylonitrile. The binder types have a strong impact on the electrode's performance. Preliminary guidelines for optimizing the performance of carbon electrodes as anodes in rechargeable lithium battery are discussed.

  13. Lithium electrode and an electrical energy storage device containing the same

    DOEpatents

    Lai, San-Cheng

    1976-07-13

    An improved lithium electrode structure comprises an alloy of lithium and silicon in specified proportions and a supporting current-collecting matrix in intimate contact with said alloy. The lithium electrode of the present invention is utilized as the negative electrode in a rechargeable electrochemical cell.

  14. Electrode architectures for efficient electronic and ionic transport pathways in high power lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Faulkner, Ankita Shah

    As the demand for clean energy sources increases, large investments have supported R&D programs aimed at developing high power lithium ion batteries for electric vehicles, military, grid storage and space applications. State of the art lithium ion technology cannot meet power demands for these applications due to high internal resistances in the cell. These resistances are mainly comprised of ionic and electronic resistance in the electrode and electrolyte. Recently, much attention has been focused on the use of nanoscale lithium ion active materials on the premise that these materials shorten the diffusion length of lithium ions and increase the surface area for electrochemical charge transfer. While, nanomaterials have allowed significant improvements in the power density of the cell, they are not a complete solution for commercial batteries. Due to their large surface area, they introduce new challenges such as a poor electrode packing densities, high electrolyte reactivity, and expensive synthesis procedures. Since greater than 70% of the cost of the electric vehicle is due to the cost of the battery, a cost-efficient battery design is most critical. To address the limitations of nanomaterials, efficient transport pathways must be engineered in the bulk electrode. As a part of nanomanufacturing research being conducted the Center for High-rate Nanomanufacturing at Northeastern University, the first aim of the proposed work is to develop electrode architectures that enhance electronic and ionic transport pathways in large and small area lithium ion electrodes. These architectures will utilize the unique electronic and mechanical properties of carbon nanotubes to create robust electrode scaffolding that improves electrochemical charge transfer. Using extensive physical and electrochemical characterization, the second aim is to investigate the effect of electrode parameters on electrochemical performance and evaluate the performance against standard commercial

  15. Rechargeable lithium sulfide electrode for a polymer tin/sulfur lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Hassoun, Jusef; Sun, Yang-Kook; Scrosati, Bruno

    In this work we investigate the electrochemical behavior of a new type of carbon-lithium sulfide composite electrode. Results based on cyclic voltammetry, charge (lithium removal)-discharge (lithium acceptance) demonstrate that this electrode has a good performance in terms of reversibility, cycle life and coulombic efficiency. XRD analysis performed in situ in a lithium cell shows that lithium sulfide can be converted into sulfur during charge and re-converted back into sulfide during the following discharge process. We also show that this electrochemical process can be efficiently carried out in polymer electrolyte lithium cells and thus, that the Li 2S-C composite can be successfully used as cathode for the development of novel types of rechargeable lithium-ion sulfur batteries where the reactive and unsafe lithium metal anode is replaced by a reliable, high capacity tin-carbon composite and the unstable organic electrolyte solution is replaced by a composite gel polymer membrane that is safe, highly conductive and able to control dendrite growth across the cell. This new Sn-C/Li 2S polymer battery operates with a capacity of 600 mAh g -1 and with an average voltage of 2 V, this leading to a value of energy density amounting to 1200 Wh kg -1.

  16. Negative electrodes for lithium cells and batteries

    DOEpatents

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

    2005-02-15

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

  17. Hierarchically porous graphene as a lithium-air battery electrode.

    PubMed

    Xiao, Jie; Mei, Donghai; Li, Xiaolin; Xu, Wu; Wang, Deyu; Graff, Gordon L; Bennett, Wendy D; Nie, Zimin; Saraf, Laxmikant V; Aksay, Ilhan A; Liu, Jun; Zhang, Ji-Guang

    2011-11-01

    The lithium-air battery is one of the most promising technologies among various electrochemical energy storage systems. We demonstrate that a novel air electrode consisting of an unusual hierarchical arrangement of functionalized graphene sheets (with no catalyst) delivers an exceptionally high capacity of 15000 mAh/g in lithium-O(2) batteries which is the highest value ever reported in this field. This excellent performance is attributed to the unique bimodal porous structure of the electrode which consists of microporous channels facilitating rapid O(2) diffusion while the highly connected nanoscale pores provide a high density of reactive sites for Li-O(2) reactions. Further, we show that the defects and functional groups on graphene favor the formation of isolated nanosized Li(2)O(2) particles and help prevent air blocking in the air electrode. The hierarchically ordered porous structure in bulk graphene enables its practical applications by promoting accessibility to most graphene sheets in this structure. PMID:21985448

  18. Aqueous processing of composite lithium ion electrode material

    SciTech Connect

    Li, Jianlin; Armstrong, Beth L; Daniel, Claus; Wood, III, David L

    2015-02-17

    A method of making a battery electrode includes the steps of dispersing an active electrode material and a conductive additive in water with at least one dispersant to create a mixed dispersion; treating a surface of a current collector to raise the surface energy of the surface to at least the surface tension of the mixed dispersion; depositing the dispersed active electrode material and conductive additive on a current collector; and heating the coated surface to remove water from the coating.

  19. Effect of contact between a current collector and a polyacetylene electrode on electrochemical behavior in polyacetylene/lithium batteries

    NASA Astrophysics Data System (ADS)

    Chen, S.-A.; Chiou, Y.-C.

    1984-05-01

    Organic batteries with a polyacetylene film (PA) as the anode, a lithium strip as the cathode, and lithium perchlorate dissolved in propylene carbonate as the electrolyte are constructed. Charging and discharging characteristics of three batteries with different types of PA electrode are investigated. Type a PA electrode involves mechanical pressed contact of nickel gauze with the upper portion of the PA electrode; charging and discharging of the battery are difficult due to the semiconducting characteristic of the PA. Type b involves a PA film which has one side coated with a sputtered palladium (Pd) film; good contact of the Pd current collector with the PA electrode makes charging and discharging easily manageable. Type c involves an iodine-doped PA film; the battery is easily charged and discharged, but cleaning the surface of the lithium electrode is necessary after a few cycles.

  20. Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries

    PubMed Central

    Shi, Feifei; Song, Zhichao; Ross, Philip N.; Somorjai, Gabor A.; Ritchie, Robert O.; Komvopoulos, Kyriakos

    2016-01-01

    Long-term durability is a major obstacle limiting the widespread use of lithium-ion batteries in heavy-duty applications and others demanding extended lifetime. As one of the root causes of the degradation of battery performance, the electrode failure mechanisms are still unknown. In this paper, we reveal the fundamental fracture mechanisms of single-crystal silicon electrodes over extended lithiation/delithiation cycles, using electrochemical testing, microstructure characterization, fracture mechanics and finite element analysis. Anisotropic lithium invasion causes crack initiation perpendicular to the electrode surface, followed by growth through the electrode thickness. The low fracture energy of the lithiated/unlithiated silicon interface provides a weak microstructural path for crack deflection, accounting for the crack patterns and delamination observed after repeated cycling. On the basis of this physical understanding, we demonstrate how electrolyte additives can heal electrode cracks and provide strategies to enhance the fracture resistance in future lithium-ion batteries from surface chemical, electrochemical and material science perspectives. PMID:27297565

  1. Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Shi, Feifei; Song, Zhichao; Ross, Philip N.; Somorjai, Gabor A.; Ritchie, Robert O.; Komvopoulos, Kyriakos

    2016-06-01

    Long-term durability is a major obstacle limiting the widespread use of lithium-ion batteries in heavy-duty applications and others demanding extended lifetime. As one of the root causes of the degradation of battery performance, the electrode failure mechanisms are still unknown. In this paper, we reveal the fundamental fracture mechanisms of single-crystal silicon electrodes over extended lithiation/delithiation cycles, using electrochemical testing, microstructure characterization, fracture mechanics and finite element analysis. Anisotropic lithium invasion causes crack initiation perpendicular to the electrode surface, followed by growth through the electrode thickness. The low fracture energy of the lithiated/unlithiated silicon interface provides a weak microstructural path for crack deflection, accounting for the crack patterns and delamination observed after repeated cycling. On the basis of this physical understanding, we demonstrate how electrolyte additives can heal electrode cracks and provide strategies to enhance the fracture resistance in future lithium-ion batteries from surface chemical, electrochemical and material science perspectives.

  2. Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries.

    PubMed

    Shi, Feifei; Song, Zhichao; Ross, Philip N; Somorjai, Gabor A; Ritchie, Robert O; Komvopoulos, Kyriakos

    2016-01-01

    Long-term durability is a major obstacle limiting the widespread use of lithium-ion batteries in heavy-duty applications and others demanding extended lifetime. As one of the root causes of the degradation of battery performance, the electrode failure mechanisms are still unknown. In this paper, we reveal the fundamental fracture mechanisms of single-crystal silicon electrodes over extended lithiation/delithiation cycles, using electrochemical testing, microstructure characterization, fracture mechanics and finite element analysis. Anisotropic lithium invasion causes crack initiation perpendicular to the electrode surface, followed by growth through the electrode thickness. The low fracture energy of the lithiated/unlithiated silicon interface provides a weak microstructural path for crack deflection, accounting for the crack patterns and delamination observed after repeated cycling. On the basis of this physical understanding, we demonstrate how electrolyte additives can heal electrode cracks and provide strategies to enhance the fracture resistance in future lithium-ion batteries from surface chemical, electrochemical and material science perspectives. PMID:27297565

  3. Electronically conductive polymer binder for lithium-ion battery electrode

    SciTech Connect

    Liu, Gao; Battaglia, Vincent S.; Park, Sang -Jae

    2015-10-06

    A family of carboxylic acid groups containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. Triethyleneoxide side chains provide improved adhesion to materials such as, graphite, silicon, silicon alloy, tin, tin alloy. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

  4. Electronically conductive polymer binder for lithium-ion battery electrode

    SciTech Connect

    Liu, Gao; Xun, Shidi; Battaglia, Vincent S.; Zheng, Honghe; Wu, Mingyan

    2015-07-07

    A family of carboxylic acid groups containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. Triethyleneoxide side chains provide improved adhesion to materials such as, graphite, silicon, silicon alloy, tin, tin alloy. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

  5. Superior lithium storage performance using sequentially stacked MnO2/reduced graphene oxide composite electrodes.

    PubMed

    Kim, Sue Jin; Yun, Young Jun; Kim, Ki Woong; Chae, Changju; Jeong, Sunho; Kang, Yongku; Choi, Si-Young; Lee, Sun Sook; Choi, Sungho

    2015-04-24

    Hybrid nanostructures based on graphene and metal oxides hold great potential for use in high-performance electrode materials for next-generation lithium-ion batteries. Herein, a new strategy to fabricate sequentially stacked α-MnO2 /reduced graphene oxide composites driven by surface-charge-induced mutual electrostatic interactions is proposed. The resultant composite anode exhibits an excellent reversible charge/discharge capacity as high as 1100 mA h g(-1) without any traceable capacity fading, even after 100 cycles, which leads to a high rate capability electrode performance for lithium ion batteries. Thus, the proposed synthetic procedures guarantee a synergistic effect of multidimensional nanoscale media between one (metal oxide nanowire) and two dimensions (graphene sheet) for superior energy-storage electrodes. PMID:25845554

  6. Manufacturing of Protected Lithium Electrodes for Advanced Lithium-Air, Lithium-Water & Lithium-Sulfur Batteries

    SciTech Connect

    Visco, Steven J

    2015-11-30

    The global demand for rechargeable batteries is large and growing rapidly. Assuming the adoption of electric vehicles continues to increase, the need for smaller, lighter, and less expensive batteries will become even more pressing. In this vein, PolyPlus Battery Company has developed ultra-light high performance batteries based on its proprietary protected lithium electrode (PLE) technology. The Company’s Lithium-Air and Lithium-Seawater batteries have already demonstrated world record performance (verified by third party testing), and we are developing advanced lithium-sulfur batteries which have the potential deliver high performance at low cost. In this program PolyPlus Battery Company teamed with Corning Incorporated to transition the PLE technology from bench top fabrication using manual tooling to a pre- commercial semi-automated pilot line. At the inception of this program PolyPlus worked with a Tier 1 battery manufacturing engineering firm to design and build the first-of-its-kind pilot line for PLE production. The pilot line was shipped and installed in Berkeley, California several months after the start of the program. PolyPlus spent the next two years working with and optimizing the pilot line and now produces all of its PLEs on this line. The optimization process successfully increased the yield, throughput, and quality of PLEs produced on the pilot line. The Corning team focused on fabrication and scale-up of the ceramic membranes that are key to the PLE technology. PolyPlus next demonstrated that it could take Corning membranes through the pilot line process to produce state-of-the-art protected lithium electrodes. In the latter part of the program the Corning team developed alternative membranes targeted for the large rechargeable battery market. PolyPlus is now in discussions with several potential customers for its advanced PLE-enabled batteries, and is building relationships and infrastructure for the transition into manufacturing. It is likely

  7. Graphene-based integrated electrodes for flexible lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Shi, Ying; Wen, Lei; Zhou, Guangmin; Chen, Jing; Pei, Songfeng; Huang, Kun; Cheng, Hui-Ming; Li, Feng

    2015-06-01

    We have prepared flexible free-standing electrodes with anode and cathode active materials deposited on a highly conductive graphene membrane by a two-step filtration method. Compared with conventional electrodes using metal as current collectors, these electrodes have displayed stronger adhesion, superior electrochemical performance, higher energy density, and better flexibility. A full lithium ion battery assembled by adopting these graphene-based electrodes has showed high rate capability and long cyclic life. We have also assembled a thin, lightweight, and flexible lithium ion battery with poly-(dimethyl siloxane) sheets as packaging material to light a red light-emitting diode. This flexible battery can be easily bent without structural failure or performance loss and operated well under a bent state. The fabrication process of these graphene-based integrated electrodes only has two filtration steps; thus it is easy to scale up. These results suggest great potential for these graphene-based flexible batteries in lightweight, bendable, and wearable electronic devices.

  8. Nanostructured lithium-aluminum alloy electrodes for lithium-ion batteries.

    SciTech Connect

    Hudak, Nicholas S.; Huber, Dale L.

    2010-12-01

    Electrodeposited aluminum films and template-synthesized aluminum nanorods are examined as negative electrodes for lithium-ion batteries. The lithium-aluminum alloying reaction is observed electrochemically with cyclic voltammetry and galvanostatic cycling in lithium half-cells. The electrodeposition reaction is shown to have high faradaic efficiency, and electrodeposited aluminum films reach theoretical capacity for the formation of LiAl (1 Ah/g). The performance of electrodeposited aluminum films is dependent on film thickness, with thicker films exhibiting better cycling behavior. The same trend is shown for electron-beam deposited aluminum films, suggesting that aluminum film thickness is the major determinant in electrochemical performance regardless of deposition technique. Synthesis of aluminum nanorod arrays on stainless steel substrates is demonstrated using electrodeposition into anodic aluminum oxide templates followed by template dissolution. Unlike nanostructures of other lithium-alloying materials, the electrochemical performance of these aluminum nanorod arrays is worse than that of bulk aluminum.

  9. Lithium storage mechanisms in purpurin based organic lithium ion battery electrodes

    PubMed Central

    Reddy, Arava Leela Mohana; Nagarajan, Subbiah; Chumyim, Porramate; Gowda, Sanketh R.; Pradhan, Padmanava; Jadhav, Swapnil R.; Dubey, Madan; John, George; Ajayan, Pulickel M.

    2012-01-01

    Current lithium batteries operate on inorganic insertion compounds to power a diverse range of applications, but recently there is a surging demand to develop environmentally friendly green electrode materials. To develop sustainable and eco-friendly lithium ion batteries, we report reversible lithium ion storage properties of a naturally occurring and abundant organic compound purpurin, which is non-toxic and derived from the plant madder. The carbonyl/hydroxyl groups present in purpurin molecules act as redox centers and reacts electrochemically with Li-ions during the charge/discharge process. The mechanism of lithiation of purpurin is fully elucidated using NMR, UV and FTIR spectral studies. The formation of the most favored six membered binding core of lithium ion with carbonyl groups of purpurin and hydroxyl groups at C-1 and C-4 positions respectively facilitated lithiation process, whereas hydroxyl group at C-2 position remains unaltered. PMID:23233879

  10. Thin film lithium-based batteries and electrochromic devices fabricated with nanocomposite electrode materials

    DOEpatents

    Gillaspie, Dane T; Lee, Se-Hee; Tracy, C. Edwin; Pitts, John Roland

    2014-02-04

    Thin-film lithium-based batteries and electrochromic devices (10) are fabricated with positive electrodes (12) comprising a nanocomposite material composed of lithiated metal oxide nanoparticles (40) dispersed in a matrix composed of lithium tungsten oxide.

  11. Lithium Wall Conditioning And Surface Dust Detection On NSTX

    SciTech Connect

    Skinner, C H; Bell, M G; Friesen, F.Q.L.; Heim, B; Jaworski, M A; Kugel, H; Maingi, R; Rais, B; Taylor, C N

    2011-05-23

    Lithium evaporation onto NSTX plasma facing components (PFC) has resulted in improved energy confinement, and reductions in the number and amplitude of edge-localized modes (ELMs) up to the point of complete ELM suppression. The associated PFC surface chemistry has been investigated with a novel plasma material interface probe connected to an in-vacuo surface analysis station. Analysis has demonstrated that binding of D atoms to the polycrystalline graphite material of the PFCs is fundamentally changed by lithium - in particular deuterium atoms become weakly bonded near lithium atoms themselves bound to either oxygen or the carbon from the underlying material. Surface dust inside NSTX has been detected in real-time using a highly sensitive electrostatic dust detector. In a separate experiment, electrostatic removal of dust via three concentric spiral-shaped electrodes covered by a dielectric and driven by a high voltage 3-phase waveform was evaluated for potential application to fusion reactors

  12. Manufacturing of advanced Li(NiMnCo)O2 electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Smyrek, P.; Pröll, J.; Rakebrandt, J.-H.; Seifert, H. J.; Pfleging, W.

    2015-03-01

    Lithium-ion batteries require an increase in cell life-time as well as an improvement in cycle stability in order to be used as energy storage systems, e.g. for stationary devices or electric vehicles. Nowadays, several cathode materials such as Li(NiMnCo)O2 (NMC) are under intense investigation to enhanced cell cycling behavior by simultaneously providing reasonable costs. Previous studies have shown that processing of three-dimensional (3D) micro-features in electrodes using nanosecond laser radiation further increases the active surface area and therefore, the lithium-ion diffusion cell kinetics. Within this study, NMC cathodes were prepared by tape-casting and laser-structured using nanosecond laser radiation. Furthermore, laser-induced breakdown spectroscopy (LIBS) was used in a first experimental attempt to analyze the lithium distribution in unstructured NMC cathodes at different state-of-charges (SOC). LIBS will be applied to laser-structured cathodes in order to investigate the lithium distribution at different SOC. The results will be compared to those obtained for unstructured electrodes to examine advantages of 3D micro-structures with respect to lithium-ion diffusion kinetics.

  13. Expansion and shrinkage of the sulfur composite electrode in rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    He, Xiangming; Ren, Jianguo; Wang, Li; Pu, Weihua; Jiang, Changyin; Wan, Chunrong

    The expansion and shrinkage characteristics of sulfur composite cathode electrode in rechargeable lithium batteries have been investigated. It was found that the sulfur composites electrodes expanded when discharging and shrank when charging again. The thickness change of the electrode was measured to be about 22%. The thickness of lithium metal anodes was also changed when lithium deposition and dissolution, while the sulfur composites electrodes expanded and shrank conversely. The investigation showed that the thickness changes of lithium anode and sulfur composite cathode could be compensated with each other to keep the total thickness of the cell not to change so much.

  14. Electrochemical effect of lithium tungsten oxide modification on LiCoO2 thin film electrode

    NASA Astrophysics Data System (ADS)

    Hayashi, Tetsutaro; Okada, Jiro; Toda, Eiji; Kuzuo, Ryuichi; Matsuda, Yasutaka; Kuwata, Naoaki; Kawamura, Junichi

    2015-07-01

    We fabricated a lithium tungsten oxide (LWO)-modified LiCoO2 (LCO) thin film electrode by pulsed laser deposition and investigated the reason for its lower resistance as compared with a bare LCO electrode. X-ray diffraction revealed that the LWO layer has a randomly oriented Li2WO4 structure with tetragonal symmetry. Scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX) indicated that the LWO modification changes the LCO particle surface, and the electrochemical impedance spectroscopy demonstrated that the LWO modification on LCO decreases the lithium ion transfer resistance at the interface between the positive electrode and the liquid electrolyte and increases the frequency factor at the interface. X-ray photoemission spectroscopy, EDX, and electron energy loss spectroscopy (EELS) indicated the presence of phosphate on the surface of the unmodified LCO electrode after electrochemical tests, but EDX and EELS did not indicate the presence of phosphate in the LWO-modified LCO electrode. The absence of phosphates apparently alleviates the hindrance of Li+ ion diffusion and increases the frequency factor in LCO, resulting in lowered Li+ ion transfer resistance at the interface.

  15. Raman diagnostics of LiCoO2 electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gross, Toni; Hess, Christian

    2014-06-01

    LiCoO2 based electrode materials were characterized in detail using visible Raman spectroscopy. The studied materials comprise the active LiCoO2 material itself as well as electrochemically relevant composites of LiCoO2 with binder and conductive additives. Spatially resolved analysis, i.e. mapping of LiCoO2 composite electrodes reveals a significant variation of chemical composition across the electrode surface. Based on wavelength-dependent studies we demonstrate the presence of a resonance enhancement for LiCoO2 materials for green laser excitation allowing for in situ studies on the LiCoO2-based electrodes during lithium de-intercalation. During in situ experiments no significant structural changes occur consistent with the fact that visible Raman spectroscopy probes mainly the surface region of the LiCoO2 composite electrode. Our results demonstrate the potential of Raman spectroscopy for spatially resolved and in situ analysis of lithium-ion batteries.

  16. Visualization of Charge Distribution in a Lithium Battery Electrode

    SciTech Connect

    Liu, Jun; Kunz, Martin; Chen, Kai; Tamura, Nobumichi; Richardson, Thomas J.

    2010-07-02

    We describe a method for direct determination and visualization of the distribution of charge in a composite electrode. Using synchrotron X-ray microdiffraction, state-of-charge profiles in-plane and normal to the current collector were measured. In electrodes charged at high rate, the signatures of nonuniform current distribution were evident. The portion of a prismatic cell electrode closest to the current collector tab had the highest state of charge due to electronic resistance in the composite electrode and supporting foil. In a coin cell electrode, the active material at the electrode surface was more fully charged than that close to the current collector because the limiting factor in this case is ion conduction in the electrolyte contained within the porous electrode.

  17. Active lithium replenishment to extend the life of a cell employing carbon and iron phosphate electrodes

    NASA Astrophysics Data System (ADS)

    Wang, John; Soukiazian, Souren; Verbrugge, Mark; Tataria, Harshad; Coates, Dwaine; Hall, David; Liu, Ping

    We describe and implement a method of extending the life of a LiFePO 4/graphite lithium ion battery by replenishing the lost active lithium during cell operation and concomitant capacity fade. The approach may prove helpful in terms of increasing lithium ion cell life. After the cell had lost 30% of its capacity, analysis showed that the cell had not experienced significant impedance increase or cathode capacity loss, and the anode had lost about 5% of its storage capacity. The analysis confirmed that the loss of active lithium greatly outpaced the loss of capacity for either electrode and is responsible for cell capacity decay. The cathode was then discharged against an external lithium electrode to increase the amount of active lithium within the cell. About half of the lost capacity was recovered, and the cell cycled for 1500 more cycles. Active lithium replenishment from a reserve electrode may be an effective method of extending the life of lithium ion batteries.

  18. Nanostructured Composite Electrodes for Lithium Batteries (Final Technical Report)

    SciTech Connect

    Meilin Liu, James Gole

    2006-12-14

    The objective of this study was to explore new ways to create nanostructured electrodes for rechargeable lithium batteries. Of particular interests are unique nanostructures created by electrochemical deposition, etching and combustion chemical vapor deposition (CCVD). Three-dimensional nanoporous Cu6Sn5 alloy has been successfully prepared using an electrochemical co-deposition process. The walls of the foam structure are highly-porous and consist of numerous small grains. This represents a novel way of creating porous structures that allow not only fast transport of gas and liquid but also rapid electrochemical reactions due to high surface area. The Cu6Sn5 samples display a reversible capacity of {approx}400 mAhg-1. Furthermore, these materials exhibit superior rate capability. At a current drain of 10 mA/cm2(20C rate), the obtainable capacity was more than 50% of the capacity at 0.5 mA/cm2 (1C rate). Highly open and porous SnO2 thin films with columnar structure were obtained on Si/SiO2/Au substrates by CCVD. The thickness was readily controlled by the deposition time, varying from 1 to 5 microns. The columnar grains were covered by nanoparticles less than 20 nm. These thin film electrodes exhibited substantially high specific capacity. The reversible specific capacity of {approx}3.3 mAH/cm2 was demonstrated for up to 80 cycles at a charge/discharge rate of 0.3 mA/cm2. When discharged at 0.9 mA/cm2, the capacity was about 2.1 mAH/cm2. Tin dioxide box beams or tubes with square or rectangular cross sections were synthesized using CCVD. The cross-sectional width of the SnO2 tubules was tunable from 50 nm to sub-micrometer depending on synthesis temperature. The tubes are readily aligned in the direction perpendicular to the substrate surface to form tube arrays. Silicon wafers were electrochemically etched to produce porous silicon (PS) with honeycomb-type channels and nanoporous walls. The diameters of the channels are about 1 to 3 microns and the depth of the

  19. Effect of local velocity on diffusion-induced stress in large-deformation electrodes of lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Yong; Zhang, Kai; Zheng, Bailin; Yang, Fuqian

    2016-07-01

    In this work, the contribution of local velocity to the resultant flux of lithium in lithium-ion battery is introduced into the diffusion equation to describe the migration of lithium in the active material of electrodes. The effect of the local velocity on the stress evolution in a spherical electrode made of silicon is analyzed, using the derived diffusion equation and nonlinear theory of elasticity. Two boundary conditions at the surface of the electrode, which represent two extreme conditions of real electrode materials, are used in the stress analysis: one is stress-free, and the other is immobile. The numerical results with the stress-free boundary condition suggest that the effect of the local velocity on the distribution of radial stress and hoop stress increases with the increase of time and the effect of the local velocity on the distribution of lithium is relatively small. In comparison with the results without the effect of the local velocity, the effect of the local velocity is negligible for the immobile boundary condition. The numerical result shows that the use of the immobile boundary condition leads to the decrease of von-Mises stress, which likely will retard the mechanical degradation of electrode and improve the electrochemical performance of lithium-ion battery.

  20. Electrode performance of romanechite for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Tsuda, Masayuki; Arai, Hajime; Nemoto, Yasue; Sakurai, Yoji

    We studied romanechite, (2×3) tunnel type manganese dioxide, as a positive electrode material for rechargeable lithium batteries. We synthesized the sample by soft chemical techniques, and its chemical composition was Ba 0.18MnO 2.10·0.42H 2O. We obtained a first discharge capacity of 120 mAh g -1 (energy density 264 mWh g -1). The capacity decreased with cycling. We examined the thermal behavior of this material, revealing its high thermal stability.

  1. Elastomeric binders for electrodes. [in secondary lithium cells

    NASA Technical Reports Server (NTRS)

    Yen, S. P. S.; Shen, D. H.; Somoano, R. B.

    1983-01-01

    The poor mechanical integrity of the cathode represents an important problem which affects the performance of ambient temperature secondary lithium cells. Repeated charge of a TiS2 cathode may give rise to stresses which disturb the electrode structure and can contribute to capacity loss. An investigation indicates that the use of an inelastic binder material, such as Teflon, aggravates the problem, and can lead to electrode disruption and poor TiS2 particle-particle contact. The feasibility of a use of elastomers as TiS2 binder materials has, therefore, been explored. It was found that elastomeric binders provide an effective approach for simplifying rechargeable cathode fabrication. A pronounced improvement in the mechanical integrity of the cathode structure contributes to a prolonged cycle life.

  2. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-07-01

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  3. Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries

    PubMed Central

    Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

    2016-01-01

    Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution. PMID:26984488

  4. Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries.

    PubMed

    Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

    2016-01-01

    Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution. PMID:26984488

  5. Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries

    NASA Astrophysics Data System (ADS)

    Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

    2016-03-01

    Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution.

  6. Discharge model for the lithium iron-phosphate electrode

    SciTech Connect

    Srinivasan, Venkat; Newman, John

    2004-02-28

    This paper develops a mathematical model for lithium intercalation and phase change in an iron phosphate-based lithium-ion cell in order to understand the cause for the low power capability of the material. The juxtaposition of the two phases is assumed to be in the form of a shrinking core, where a shell of one phase covers a core of the second phase. Diffusion of lithium through the shell and the movement of the phase interface are described and incorporated into a porous electrode model consisting of two different particle sizes. Open-circuit measurements are used to estimate the composition ranges of the single-phase region. Model-experimental comparisons under constant current show that ohmic drops in the matrix phase, contact resistances between the current collector and the porous matrix, and transport limitations in the iron phosphate particle limit the power capability of the cells. Various design options, consisting of decreasing the ohmic drops, using smaller particles, and substituting the liquid electrolyte by a gel are explored, and their relative importance discussed. The model developed in this paper can be used as a means of optimizing the cell design to suit a particular application.

  7. Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution

    PubMed Central

    Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

    2016-01-01

    Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances. PMID:27193448

  8. Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution

    NASA Astrophysics Data System (ADS)

    Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

    2016-05-01

    Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances.

  9. Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution.

    PubMed

    Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

    2016-01-01

    Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances. PMID:27193448

  10. Electrochemical Study of Hollow Carbon Nanospheres as High-Rate and Low Temperature Negative Electrodes for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Cox, Jonathan David

    The continued advancements in portable electronics have demanded more advanced power sources. To date, lithium ion batteries have been the state-of-the-art for portable devices. One significant drawback of lithium ion batteries is the slow charging times and their performance at low temperatures. In this dissertation, we explore the electrochemical behavior of a new lithium ion, negative electrode active material, hollow carbon nanospheres (HCNS). HCNS are ˜50 nm in diameter hollow spheres with ˜5 - 10 nm graphic walls which have a nominal reversible capacity of ˜220 mAh/g. We assembled and cycled HCNS as a lithium ion anode material and compared it to graphite, currently used as the anode material in most commercial lithium ion batteries. The charging mechanism of HCNS is an intercalation of the lithium ions into the graphitic walls of the spheres, similar to graphite, determined by diffraction and electroanalytical techniques. However, the HCNS electrodes cycled at much higher charge and discharge rates than graphite. Additionally, we demonstrated HCNS cycling at low temperatures (-20 *C) in electrolytes not obtainable by graphite due to material exfoliation during cycling. Although, due to the large surface area of HCNS, the first cycle coulombic losses are very high. This work has resulted in an understanding of a potentially new lithium ion battery anode material with significantly better cycling attributes than the current anode material.

  11. Development of a benchmarking model for lithium battery electrodes

    NASA Astrophysics Data System (ADS)

    Bergholz, Timm; Korte, Carsten; Stolten, Detlef

    2016-07-01

    This paper presents a benchmarking model to enable systematic selection of anode and cathode materials for lithium batteries in stationary applications, hybrid and battery electric vehicles. The model incorporates parameters for energy density, power density, safety, lifetime, costs and raw materials. Combinations of carbon anodes, Li4Ti5O12 or TiO2 with LiFePO4 cathodes comprise interesting combinations for application in hybrid power trains. Higher cost and raw material prioritization of stationary applications hinders the breakthrough of Li4Ti5O12, while a combination of TiO2 and LiFePO4 is suggested. The favored combinations resemble state-of-the-art materials, whereas novel cell chemistries must be optimized for cells in battery electric vehicles. In contrast to actual research efforts, sulfur as a cathode material is excluded due to its low volumetric energy density and its known lifetime and safety issues. Lithium as anode materials is discarded due to safety issues linked to electrode melting and dendrite formation. A high capacity composite Li2MnO3·LiNi0.5Co0.5O2 and high voltage spinel LiNi0.5Mn1.5O4 cathode with silicon as anode material promise high energy densities with sufficient lifetime and safety properties if electrochemical and thermal stabilization of the electrolyte/electrode interfaces and bulk materials is achieved. The model allows a systematic top-down orientation of research on lithium batteries.

  12. Neutron Depth Profiling benchmarking and analysis of applications to lithium ion cell electrode and interfacial studies research

    NASA Astrophysics Data System (ADS)

    Whitney, Scott M.

    at different current rates. The results conclude that NDP is a valuable asset to the characterization of the Solid Electrolyte Interface (SEI) growth as a function of storage time. The NDP results were able to conclude that LiFePO4 cell anodes have a factor of 21 times slower rate of SEI growth than anodes from LiFePSO 4. This indicates that the capacity fade of the LiFePO4 cell will be less than that of the LiFePSO4 cell due to storage at 50°C. Furthermore, NDP was able to conclude that cycling of cells had little effect on the lithium concentration within the cathode materials. The lithium concentration was found to be uniform throughout the first 10 mum of the LiFePO4 and LiNi1/3Mn1/3Co1/3O 2 cathodes. These measurements agreed with the initial hypothesis. However, NDP analysis of cells charged at different current rates found that lithium was concentrating within the first 2 mum of the cathode's surface at the electrode-electrolyte interface. This was an unexpected conclusion, but the results also concluded that effect of the lithium concentrating near the surface is amplified by charging the cells at higher current rates. The ultimate conclusion of this research was that NDP is capable of providing invaluable insight to the behavior of lithium within the electrodes of lithium ion cells. It is the author's conclusion that NDP may be most useful in the investigation of SEI layers and their variation according to electrode composition, electrolyte compositions, and the conditions, such as temperature, to which the cells are exposed.

  13. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

    NASA Astrophysics Data System (ADS)

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-09-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

  14. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes.

    PubMed

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-01-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li(+) depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm(-2) and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm(-2) for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li(+) transport) and single ionic ionomer (prevention of Li(+) depletion). PMID:26411701

  15. Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

    PubMed Central

    Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

    2015-01-01

    The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

  16. Research on spray-dried lithium titanate as electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wen, Zhaoyin; Gu, Zhonghua; Huang, Shahua; Yang, Jianhua; Lin, Zuxiang; Yamamoto, Osamu

    Li 4Ti 5O 12 has been considered as a promising electrode material for lithium secondary batteries. In this work a spray drying process was developed to prepare porous and spherical Li 4Ti 5O 12 powders with Li 2CO 3 and rutile type TiO 2 as precursors and PVB as forming agent of pores. The experimental results showed that porous and spherical morphology of the spray-dried powders was maintained during the sintering and the subsequent heat treatment. The oxygen atmosphere was demonstrated important to the electrochemical performance of the Li 4Ti 5O 12 powders. However, overtime heat treatment would result in superfluous loss of lithium content and therefore led to obvious decrease of charge and discharge capacities.

  17. Electrochemical behaviors of a Li3N modified Li metal electrode in secondary lithium batteries

    NASA Astrophysics Data System (ADS)

    Wu, Meifen; Wen, Zhaoyin; Liu, Yu; Wang, Xiuyan; Huang, Lezhi

    2011-10-01

    A lithium conductive Li3N film is successfully prepared on Li metal surface by the direct reaction between Li and N2 gas at room temperature. X-ray diffraction (XRD), Auger electron spectroscopy (AES), cyclic voltammetry (CV), scanning electron microscopy (SEM), AC impedance, cathodic polarization and galvanostatic charge/discharge cycling tests are applied to characterize the film. The experimental results show that the Li3N protective film is tight and dense with high stability in the electrolyte. Its thickness is more than 159.4 nm and much bigger than that of a native SEI film formed on the lithium surface as received. An exchange current as low as 3.244 × 10-7 A demonstrates the formation of a complete SEI film at the electrode|electrolyte interface with Li3N modification. The SEI film is very effective in preventing the corrosion of the Li electrode in liquid electrolyte, leading to a decreased Li|electrolyte interface resistance and an average short distance of 3.16 × 10-3 cm for Li ion diffusion from electrolyte to Li surface. The Li cycling efficiency depends on N2 exposing time and is obviously enhanced by the Li3N (1 h) modification. After cycling, a dense and homogeneous Li layer deposits on the Li3N (1 h) modified Li surface, instead of a loose and inhomogeneous layer on the Li surface as received.

  18. Surface characterization of platinum electrodes.

    PubMed

    Solla-Gullón, José; Rodríguez, Paramaconi; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2008-03-14

    The quantitative analysis of the different surface sites on platinum samples is attempted from pure voltammetric data. This analysis requires independent knowledge of the fraction of two-dimensional (111) and (100) domains. Specific site-probe reactions are employed to achieve this goal. Irreversibly-adsorbed bismuth and tellurium have been revealed to be sensitive to the presence of (111) terrace domains of different width whereas almost all sites involved in (100) ordered domains have been characterized through germanium adatoms. The experimental protocol follows that used with well-defined single-crystal electrodes and, therefore, requires careful control of the surface cleanliness. Platinum basal planes and their vicinal stepped surfaces have been employed to obtain calibration plots between the charge density measured under the adatom redox peak, specific for the type of surface site, and the corresponding terrace size. The evaluation of the (100) bidimensional domains can also be achieved using the voltammetric profiles, once the fraction of (111) ordered domains present in the polyoriented platinum has been determined and their featureless contribution has been subtracted from the whole voltammetric response. Using that curve, it is possible to perform a deconvolution of the adsorption states of the polycrystalline sample different from those related to (111) domains. The fraction of (100)-related states in the deconvoluted voltammogram can then be compared to that expected from the independent estimation coming from the charge involved in the redox process undergone by the irreversibly-adsorbed germanium and thus check the result of the deconvolution. The information about the surface-site distribution can also be applied to analyze the voltammetric profile of nanocrystalline platinum electrodes. PMID:18309392

  19. A stable graphite negative electrode for the lithium-sulfur battery.

    PubMed

    Jeschull, Fabian; Brandell, Daniel; Edström, Kristina; Lacey, Matthew J

    2015-12-14

    Efficient, reversible lithium intercalation into graphite in ether-based electrolytes is enabled through a protective electrode binder, polyacrylic acid sodium salt (PAA-Na). In turn, this enables the creation of a stable "lithium-ion-sulfur" cell, using a lithiated graphite negative electrode with a sulfur positive electrode, using the common DME:DOL solvent system suited to the electrochemistry of the lithium-sulfur battery. Graphite-sulfur lithium-ion cells show average coulombic efficiencies of ∼99.5%, compared with <95% for lithium-sulfur cells, and significantly better capacity retention, taking into account cell balancing considerations. The high efficiency derives from the considerably better interfacial stability of the graphite electrode, which suppresses the polysulfide redox shuttle and self-discharge. PMID:26451894

  20. Evaluation residual moisture in lithium-ion battery electrodes and its effect on electrode performance

    DOE PAGESBeta

    Li, Jianlin; Daniel, Claus; Wood, III, David L.; An, Seong Jin

    2016-01-11

    Removing residual moisture in lithium-ion battery electrodes is essential for desired electrochemical performance. In this manuscript, the residual moisture in LiNi0.5Mn0.3Co0.2O2 cathodes produced by conventional solvent-based and aqueous processing is characterized and compared. The electrochemical performance has also been investigated for various residual moisture contents. As a result, it has been demonstrated that the residual moisture lowers the first cycle coulombic efficiency, but its effect on short term cycle life is insignificant.

  1. Emulsion-derived lithium manganese oxide powder for positive electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lu, Chung-Hsin; Lin, Shang-Wei

    Lithium manganese oxide (LiMn 2O 4) used as a positive-electrode material in lithium-ion batteries is prepared by a new water-in-oil emulsion process. An aqueous solution containing lithium and manganese cations is emulsified in kerosene by adding sorbitan monooleate as the surfactant. When the precursor solution is agitated by a magnetic mixer, impure products are obtained. LiMn 2O 4 is formed along with residual Mn 2O 3 at elevated temperatures because of insufficient dispersion and mixing of the reactive cations. When a homogenizer with a greater agitation speed is used, however, a well-mixed precursor solution is prepared, and pure LiMn 2O 4 with a Fd 3 m structure is synthesized after calcination at 800°C for 1 h. LiMn 2O 4 powder prepared by the homogenizer has higher crystallinity, smaller particle size, and narrower size distribution than that prepared by the magnetic stirrer. Compared with powder prepared by the solid-state method, the LiMn 2O 4 powder exhibits smaller particle size and less agglomeration. Moreover, the emulsion process significantly shortens the heating time required. The prepared LiMn 2O 4 powder has a high discharge capacity (120.4 mA h g -1) on the first cycle and good cycleability.

  2. Electrochromic & magnetic properties of electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zheng-Fei, Guo; Kun, Pan; Xue-Jin, Wang

    2016-01-01

    Progress in electrochromic lithium ion batteries (LIBs) is reviewed, highlighting advances and possible research directions. Methods for using the LIB electrode materials’ magnetic properties are also described, using several examples. Li4Ti5O12 (LTO) film is discussed as an electrochromic material and insertion compound. The opto-electrical properties of the LTO film have been characterized by electrical measurements and UV-Vis spectra. A prototype bi-functional electrochromic LIB, incorporating LTO as both electrochromic layer and anode, has also been characterized by charge- discharge measurements and UV-Vis transmittance. The results show that the bi-functional electrochromic LIB prototype works well. Magnetic measurement has proven to be a powerful tool to evaluate the quality of electrode materials. We introduce briefly the magnetism of solids in general, and then discuss the magnetic characteristics of layered oxides, spinel oxides, olivine phosphate LiFePO4, and Nasicon-type Li3Fe2(PO4)3. We also discuss what kind of impurities can be detected, which will guide us to fabricate high quality films and high performance devices. Project supported by the National High Technology Research and Development Program of China (Grant No. 2015AA034201) and the Chinese Universities Scientific Fund (Grant No. 2015LX002).

  3. Highly Oriented Carbon Nanotube Sheets for Rechargeable Lithium Oxygen Battery Electrodes.

    PubMed

    Ryu, Seongwoo; Kim, Byung Gon; Choi, Jang Wook; Lee, Haeshin

    2015-10-01

    Lithium oxygen batteries are one of the next generation rechargeable batteries. High energy density of lithium oxygen batteries have been considered as a very attractive power option for electric vehicles and many other electronic devices. However, they still faced substantial challenges such as short cycle life, large voltage hysteresis, low gravimetric and volumetric power. Here we developed a highly aligned CNT structured sheet for favorable lithium oxygen cathode electrodes. We fabricated highly oriented CNT sheets by rolling vertically aligned CNT arrays. Highly oriented CNT sheets provide excellent electrical conductivity with favorable mesoporous structure for cathode electrode. As a result, the CNT sheet performed maximum discharging capacity of 1810 mA/gc. We found that electrical conductivity and pore distribution plays important rolls for improving performance in lithium oxygen batteries. This study suggests new strategies of designing highly efficient porous carbon electrodes for lithium oxygen batteries. PMID:26726383

  4. Effect of covalently bonded polysiloxane multilayers on the electrochemical behavior of graphite electrode in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Pan, Qinmin; Jiang, Yinghua

    Polysiloxane multilayers were covalently bonded to the surface of natural graphite particles via diazonium chemistry and silylation reaction. The as-prepared graphite exhibited excellent discharge-charge behavior as negative electrode materials in lithium ion batteries. The improvement in the electrochemical performance of the graphite electrodes was attributed to the formation of a stable and flexible passive film on their surfaces. It was also revealed that the chemical compositions of the multilayers exerted influence on the electrochemical behavior of the graphite electrodes. The result of this study presents a new strategy to the formation of elastic and strong passive film on the graphite electrode via molecular design. Owing to the diversity of polysilxoane multilayers, this method also enables researchers to control the surface chemistries of carbonaceous materials with flexibility.

  5. High performance binderless TiO2 nanowire arrays electrode for lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Li, Yueming; Lv, Xiaojun; Li, Jinghong

    2009-09-01

    Binderless lithium ion battery electrode fabricated by anodizing Ti foil, in which TiO2 nanowire serves as active materials and unreacted Ti foil as the current collector, exhibited high electrochemical performance.

  6. Elegant design of electrode and electrode/electrolyte interface in lithium-ion batteries by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Liu, Jian; Sun, Xueliang

    2015-01-01

    Lithium-ion batteries (LIBs) are very promising power supply systems for a variety of applications, such as electric vehicles, plug-in hybrid electric vehicles, grid energy storage, and microelectronics. However, to realize these practical applications, many challenges need to be addressed in LIBs, such as power and energy density, cycling lifetime, safety, and cost. Atomic layer deposition (ALD) is emerging as a powerful technique for solving these problems due to its exclusive advantages over other film deposition counterparts. In this review, we summarize the state-of-the-art progresses of employing ALD to design novel nanostructured electrode materials and solid-state electrolytes and to tailor electrode/electrolyte interface by surface coatings in order to prevent unfavorable side reactions and achieve optimal performance of the electrode. Insights into the future research and development of the ALD technique for LIB applications are also discussed. We expect that this review article will provide resourceful information to researchers in both fields of LIBs and ALD and also will stimulate more insightful studies of using ALD for the development of next-generation LIBs.

  7. Elegant design of electrode and electrode/electrolyte interface in lithium-ion batteries by atomic layer deposition.

    PubMed

    Liu, Jian; Sun, Xueliang

    2015-01-16

    Lithium-ion batteries (LIBs) are very promising power supply systems for a variety of applications, such as electric vehicles, plug-in hybrid electric vehicles, grid energy storage, and microelectronics. However, to realize these practical applications, many challenges need to be addressed in LIBs, such as power and energy density, cycling lifetime, safety, and cost. Atomic layer deposition (ALD) is emerging as a powerful technique for solving these problems due to its exclusive advantages over other film deposition counterparts. In this review, we summarize the state-of-the-art progresses of employing ALD to design novel nanostructured electrode materials and solid-state electrolytes and to tailor electrode/electrolyte interface by surface coatings in order to prevent unfavorable side reactions and achieve optimal performance of the electrode. Insights into the future research and development of the ALD technique for LIB applications are also discussed. We expect that this review article will provide resourceful information to researchers in both fields of LIBs and ALD and also will stimulate more insightful studies of using ALD for the development of next-generation LIBs. PMID:25514580

  8. Thermal-stability studies of electrode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Jiang, Junwei

    2005-07-01

    The thermal stability of lithium-ion batteries has recently attracted attention for two major reasons. (1) Attempts to make large-size cells used in power tools, E-bikes and EVs. Large cells have lower surface area to volume ratios and hence heat dissipation is more problematic than 18650-size cells. Safety problems, therefore, for large cells are more serious. (2) Next generation high-capacity electrodes will increase the energy density of lithium-ion cells meaning even an 18650-size cell may face safety concerns. This thesis presents studies of the thermal stability of electrode materials in electrolytes to understand their reactivity. A search for new positive electrode materials with high thermal stability was made. The thermal stability of two common electrode materials (Li0.81 C6 and Li0.5CoO2) in lithium-ion cells was studied by Accelerating Rate Calorimeter (ARC). Li0.81C 6 has much lower reactivity with lithium bis(oxalato)borate (LiBOB) electrolyte compared to LiPF6 electrolyte. It is not the case, however, for Li0.5CoO2. Oven tests of full LiCoO 2/C 18650-size cells with LiBOB or LiPF6 electrolytes, confirmed the ARC results. ARC was then used to study the reactivity of existing electrode materials. The thermal stability of a negative electrode material was found to increase with the binding energy of Li atoms hosted in the material. Li0.5VO 2 (B) has a higher lithium binding energy (2.45 eV vs. Li) than Li 0.81C6 (0.1 eV vs. Li) and Li7Ti5O 12 (1.55 eV) and it shows the highest thermal stability in EC/DEC among the three materials. The reactivity of two existing positive electrode materials, LiMn2O4 and LiFePO4, was studied. Cell systems expected to be highly tolerant to thermal abuse were suggested: LiFePO 4/C or Li4Ti5O12 in LiBOB electrolytes. The system, x Li[Ni1/2Mn1/2]O2 • y LiCoO2 • z Li[Li1/3Mn2/3]O2 (x + y + z = 1), was explored for new positive electrode materials with large capacity and high thermal stability. Li[(Ni0.5Mn0.5) xCo1-x]O2 (0

  9. The surface states of lithium tetraborate

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Mei, Wai-Ning; Dowben, Peter A.

    2013-01-01

    The different low index surface terminations of lithium tetraborate, Li2B4O7, are dominated by electronic states that fall within the band gap of the projection of the bulk states. As a pyroelectric material, lithium tetraborate, Li2B4O7, is a wide band gap dielectric, yet the (110) surface has a much smaller band gap because of occupied surface states that fall at binding energies between the valence band maximum and the Fermi level. The (100) surface is dominated, however, by unoccupied surface states that also fall in the gap between the conduction band minimum and the valence band maximum, but at binding energies just below the conduction band minimum. These very different types of surface states are consistent with the assignment of occupied surface states to states that are observed near the Fermi level in photoemission studies of Li2B4O7(110). The unoccupied surface states are also seen to be consistent with the inverse photoemission spectra of Li2B4O7(100). Clearly, the different surface terminations of lithium tetraborate yield very different types of surface electronic states.

  10. Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl).

    PubMed

    Guo, Yang; Li, Feng; Zhu, Haochen; Li, Guangming; Huang, Juwen; He, Wenzhi

    2016-05-01

    Spent lithium-ion batteries (LIBs) are considered as an important secondary resource for its high contents of valuable components, such as lithium and cobalt. Currently, studies mainly focus on the recycling of cathode electrodes. There are few studies concentrating on the recovery of anode electrodes. In this work, based on the analysis result of high amount of lithium contained in the anode electrode, the acid leaching process was applied to recycle lithium from anode electrodes of spent LIBs. Hydrochloric acid was introduced as leaching reagent, and hydrogen peroxide as reducing agent. Within the range of experiment performed, hydrogen peroxide was found to have little effect on lithium leaching process. The highest leaching recovery of 99.4wt% Li was obtained at leaching temperature of 80°C, 3M hydrochloric acid and S/L ratio of 1:50g/ml for 90min. The graphite configuration with a better crystal structure obtained after the leaching process can also be recycled. PMID:26674969

  11. The origin of high electrolyte-electrode interfacial resistances in lithium cells containing garnet type solid electrolytes.

    PubMed

    Cheng, Lei; Crumlin, Ethan J; Chen, Wei; Qiao, Ruimin; Hou, Huaming; Franz Lux, Simon; Zorba, Vassilia; Russo, Richard; Kostecki, Robert; Liu, Zhi; Persson, Kristin; Yang, Wanli; Cabana, Jordi; Richardson, Thomas; Chen, Guoying; Doeff, Marca

    2014-09-14

    Dense LLZO (Al-substituted Li7La3Zr2O12) pellets were processed in controlled atmospheres to investigate the relationships between the surface chemistry and interfacial behavior in lithium cells. Laser induced breakdown spectroscopy (LIBS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, synchrotron X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS) studies revealed that Li2CO3 was formed on the surface when LLZO pellets were exposed to air. The distribution and thickness of the Li2CO3 layer were estimated by a combination of bulk and surface sensitive techniques with various probing depths. First-principles thermodynamic calculations confirmed that LLZO has an energetic preference to form Li2CO3 in air. Exposure to air and the subsequent formation of Li2CO3 at the LLZO surface is the source of the high interfacial impedances observed in cells with lithium electrodes. Surface polishing can effectively remove Li2CO3 and dramatically improve the interfacial properties. Polished samples in lithium cells had an area specific resistance (ASR) of only 109 Ω cm(2) for the LLZO/Li interface, the lowest reported value for Al-substituted LLZO. Galvanostatic cycling results obtained from lithium symmetrical cells also suggest that the quality of the LLZO/lithium interface has a significant impact on the device lifetime. PMID:25057850

  12. Surface analysis of lithium coatings in NSTX

    NASA Astrophysics Data System (ADS)

    Timberlake, J.; Kugel, H. W.; Skinner, C. H.; Yao, N.

    2007-11-01

    Lithium coatings have been applied to NSTX plasma facing surfaces as part of a long term program to explore the potential for lithium to improve plasma and PFC performance. A LIThium EvaporatoR (LITER) directed a collimated stream of lithium vapor from an upper vacuum vessel port toward the graphite tiles of the lower center stack and divertor either before, or continuously between and during, discharges. Silicon witness coupons and other samples were retrieved from the vacuum vessel after the campaign and the surface morphology and elemental compostion examined with a XL30 FEG-SEM microscope equipped with an energy dispersed X-rays system sensitive to elements with atomic number greater than 4. The surfaces showed a complex morphology with nucleation sites apparent. Carbon and oxygen were the dominant impurities. Trace metals (Fe and Cr) were detected in the coating on the Si coupon, but not in a flake of bulk Li. We will present results of the surface analysis of samples exposed to Li evaporation in NSTX.

  13. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    DOE PAGESBeta

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition bymore » X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.« less

  14. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    SciTech Connect

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.

  15. Li(V0.5Ti0.5)S2 as a 1 V lithium intercalation electrode

    NASA Astrophysics Data System (ADS)

    Clark, Steve J.; Wang, Da; Armstrong, A. Robert; Bruce, Peter G.

    2016-03-01

    Graphite, the dominant anode in rechargeable lithium batteries, operates at ~0.1 V versus Li+/Li and can result in lithium plating on the graphite surface, raising safety concerns. Titanates, for example, Li4Ti5O12, intercalate lithium at~1.6 V versus Li+/Li, avoiding problematic lithium plating at the expense of reduced cell voltage. There is interest in 1 V anodes, as this voltage is sufficiently high to avoid lithium plating while not significantly reducing cell potential. The sulfides, LiVS2 and LiTiS2, have been investigated as possible 1 V intercalation electrodes but suffer from capacity fading, large 1st cycle irreversible capacity or polarization. Here we report that the 50/50 solid solution, Li1+x(V0.5Ti0.5)S2, delivers a reversible capacity to store charge of 220 mAhg-1 (at 0.9 V), 99% of theoretical, at a rate of C/2, retaining 205 mAhg-1 at C-rate (92% of theoretical). Rate capability is excellent with 200 mAhg-1 at 3C. C-rate is discharge in 1 h. Polarization is low, 100 mV at C/2. To the best of our knowledge, the properties/performances of Li(V0.5Ti0.5)S2 exceed all previous 1 V electrodes.

  16. Mechanics of high-capacity electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Ting, Zhu

    2016-01-01

    Rechargeable batteries, such as lithium-ion batteries, play an important role in the emerging sustainable energy landscape. Mechanical degradation and resulting capacity fade in high-capacity electrode materials critically hinder their use in high-performance lithium-ion batteries. This paper presents an overview of recent advances in understanding the electrochemically-induced mechanical behavior of the electrode materials in lithium-ion batteries. Particular emphasis is placed on stress generation and facture in high-capacity anode materials such as silicon. Finally, we identify several important unresolved issues for future research. Project support by the NSF (Grant Nos. CMMI 1100205 and DMR 1410936).

  17. Roles of transition metals interchanging with lithium in electrode materials.

    PubMed

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Tokuda, Kazuya; Sakaida, Masashi; Ichitsubo, Tetsu; Oishi, Masatsugu; Mizuki, Jun'ichiro; Matsubara, Eiichiro

    2015-06-01

    Roles of antisite transition metals interchanging with Li atoms in electrode materials of Li transition-metal complex oxides were clarified using a newly developed direct labeling method, termed powder diffraction anomalous fine structure (P-DAFS) near the Ni K-edge. We site-selectively investigated the valence states and local structures of Ni in Li0.89Ni1.11O2, where Ni atoms occupy mainly the NiO2 host-layer sites and partially the interlayer Li sites in-between the host layers, during electrochemical Li insertion/extraction in a lithium-ion battery (LIB). The site-selective X-ray near edge structure evaluated via the P-DAFS method revealed that the interlayer Ni atoms exhibited much lower electrochemical activity as compared to those at the host-layer site. Furthermore, the present analyses of site-selective extended X-ray absorption fine structure performed using the P-DAFS method indicates local structural changes around the residual Ni atoms at the interlayer space during the initial charge; it tends to gather to form rock-salt NiO-like domains around the interlayer Ni. The presence of the NiO-like domains in the interlayer space locally diminishes the interlayer distance and would yield strain energy because of the lattice mismatch, which retards the subsequent Li insertion both thermodynamically and kinetically. Such restrictions on the Li insertion inevitably make the NiO-like domains electrochemically inactive, resulting in an appreciable irreversible capacity after the initial charge but an achievement of robust linkage of neighboring NiO2 layers that tend to be dissociated without the Li occupation. The P-DAFS characterization of antisite transition metals interchanging with Li atoms complements the understanding of the detailed charge-compensation and degradation mechanisms in the electrode materials. PMID:25959625

  18. Mesoporous α-MnO 2/Pd catalyst air electrode for rechargeable lithium-air battery

    NASA Astrophysics Data System (ADS)

    Thapa, Arjun Kumar; Ishihara, Tatsumi

    Rechargeable lithium-air battery is studied using Pd/mesoporous α-MnO 2 air composite electrode. In the present work, we have studied the preparation and electrochemical performance of ordered mesoporous α-MnO 2 as a cathode catalyst for rechargeable Li-air batteries. α-MnO 2 was prepared by reduction of KMnO 4 solution in acidic aqueous solution followed by successive proton and alkali-ion exchange method. α-MnO 2 with high surface area of 33-133.0 m 2 g -1 was successively synthesized and used as an electrode catalyst for Li-air battery. It was found that the mixture of Pd and mesoporous α-MnO 2 electrode shows the high activity to oxidation and reduction of Li to form Li 2O 2 or Li 2O. Application of Pd/mesoporous α-MnO 2, which is mixed with teflonized acetylene binder (TAB), for air electrode is effective for decreasing the charge potential and also improved the energy efficiency as well as cyclability.

  19. Vertically-aligned carbon nanotubes on aluminum as a light-weight positive electrode for lithium-polysulfide batteries.

    PubMed

    Liatard, S; Benhamouda, K; Fournier, A; Ramos, R; Barchasz, C; Dijon, J

    2015-05-01

    A light-weight, high specific surface current collector made of vertically-aligned carbon nanotubes grown on an aluminum substrate was fabricated and studied as a positive electrode in a semi-liquid lithium/polysulfide battery. This simple system delivered stable capacities over 1000 mA h gS(-1) and 2 mA h cm(-2) with almost no capacity loss over 50 cycles. PMID:25853546

  20. Conductive Polymer-Coated VS4 Submicrospheres As Advanced Electrode Materials in Lithium-Ion Batteries.

    PubMed

    Zhou, Yanli; Li, Yanlu; Yang, Jing; Tian, Jian; Xu, Huayun; Yang, Jian; Fan, Weiliu

    2016-07-27

    VS4 as an electrode material in lithium-ion batteries holds intriguing features like high content of sulfur and one-dimensional structure, inspiring the exploration in this field. Herein, VS4 submicrospheres have been synthesized via a simple solvothermal reaction. However, they quickly degrade upon cycling as an anode material in lithium-ion batteries. So, three conductive polymers, polythiophene (PEDOT), polypyrrole (PPY), and polyaniline (PANI), are coated on the surface to improve the electron conductivity, suppress the diffusion of polysulfides, and modify the interface between electrode/electrolyte. PANI is the best in the polymers. It improves the Coulombic efficiency to 86% for the first cycle and keeps the specific capacity at 755 mAh g(-1) after 50 cycles, higher than the cases of naked VS4 (100 mAh g(-1)), VS4@PEDOT (318 mAh g(-1)), and VS4@PPY (448 mAh g(-1)). The good performances could be attributed to the improved charge-transfer kinetics and the strong interaction between PANI and VS4 supported by theoretical simulation. The discharge voltage ∼2.0 V makes them promising cathode materials. PMID:27377263

  1. Lithium insertion into mesoscopic and single-crystal TiO{sub 2} (rutile) electrodes

    SciTech Connect

    Kavan, L.; Fattakhova, D.; Krtil, P.

    1999-04-01

    Electrochemical behavior of single-crystal and mesoscopic TiO{sub 2} (rutile) was studied in propylene carbonate solutions at potentials negative to the flatband potential. In electrolytic solutions containing sodium or tetrabutylammonium (Bu{sub 4}N{sup +}), the injected charge is compensated by protonization of the surface and/or by adsorption of cations in the double layer. In electrolytic solutions containing Li{sup +}, the insertion into the rutile lattice occurs at potentials below 1.5 V (Li/Li{sup +}). At higher potentials, the charge is compensated mainly by a nonfaradaic process. Lithium insertion into rutile proceeds at a potential ca. 0.4 V more negative than the insertion potential into anatase. The maximum insertion capacity of rutile is also lower than that of anatase. The insertion of lithium into rutile is accompanied by an increase of the electrode mass, while the mass/charge relations show hystereses between anodic and cathodic potential sweeps. This behavior is explained in terms of a free convection in the electrode vicinity.

  2. Electrochemical and impedance investigation of the effect of lithium malonate on the performance of natural graphite electrodes in lithium-ion batteries

    SciTech Connect

    Sun, Xiao-Guang; Dai, Sheng

    2010-01-01

    Lithium malonate (LM) was coated on the surface of a natural graphite (NG) electrode, which was then tested as the negative electrode in the electrolytes of 0.9 M LiPF6/EC-PC-DMC (1/1/3, by weight) and 1.0 M LiBF4/EC-PC-DMC (1/1/3, by weight) under a current density of 0.075 mA cm-2. LM was also used as an additive to the electrolyte of 1.0 M LiPF6/EC-DMC-DEC (1/1/1, by volume) and tested on a bare graphite electrode. It was found that both the surface coating and the additive approach were effective in improving first charge discharge capacity and coulomb efficiency. Electrochemical impedance spectra showed that the decreased interfacial impedance was coupled with improved coulomb efficiency of the cells using coated graphite electrodes. Cyclic voltammograms (CVs) on fresh bare and coated natural graphite electrodes confirmed that all the improvement in the half-cell performance was due to the suppression of the solvent decomposition through the surface modification with LM. The CV data also showed that the carbonate electrolyte with LM as the additive was not stable against oxidation, which resulted in lower capacity of the full cell with commercial graphite and LiCoO2 electrodes.

  3. Optimized Silicon Electrode Architecture, Interface, and Microgeometry for Next-Generation Lithium-Ion Batteries.

    PubMed

    Molina Piper, Daniela; Evans, Tyler; Xu, Shanshan; Kim, Seul Cham; Han, Sang Sub; Liu, Ken Liang; Oh, Kyu Hwan; Yang, Ronggui; Lee, Se-Hee

    2016-01-01

    Optimized performance of silicon-ionic- liquid lithium-ion batteries through the implementation of a new electrode-microgeometry. The incorporation of 1D silicon nanowires into the cyclized-polyacrylonitrile-based electrode-architecture allows for greatly improved active material utilization, higher rate capabilities, and reduced interfacial reactions. PMID:26506084

  4. Si composite electrode with Li metal doping for advanced lithium-ion battery

    SciTech Connect

    Liu, Gao; Xun, Shidi; Battaglia, Vincent

    2015-12-15

    A silicon electrode is described, formed by combining silicon powder, a conductive binder, and SLMP.TM. powder from FMC Corporation to make a hybrid electrode system, useful in lithium-ion batteries. In one embodiment the binder is a conductive polymer such as described in PCT Published Application WO 2010/135248 A1.

  5. Surface characterization of electodes from high-power lithium-oin batteries.

    SciTech Connect

    Andersson, A. M.; Abraham, D. P.; Liu, J.; Amine, K.; Haach, R.; MacLaren, S.; Chemical Engineering; Univ. of Illinois; Angstrom Lab.

    2002-10-01

    X-ray photoelectron spectroscopy and scanning electron microscopy were used to study electrode samples obtained from 18650-type lithium-ion cells subjected to accelerated calendar-life testing at temperatures ranging from 25 to 70 C and at states-of-charge from 40 to 80%. The cells contained LiNi{sub 0.8}Co{sub 0.2}O{sub 2}-based positive electrodes (cathodes), graphite-based negative electrodes (anodes), and a 1 M LiPF{sub 6} ethylene carbonate:diethyl carbonate (1:1) electrolyte. The results from electrochemically treated samples showed surface film formation on both electrodes. The positive electrode laminate surfaces contained a mixture of organic species that included polycarbonates, and LiF, Li{sub x}PF{sub y}-type and Li{sub x}PF{sub y}O{sub z}-type compounds. The same surface compounds were observed regardless of test temperature, test duration, and state-of-charge. On the negative electrode laminates lithium alkyl carbonates (ROCO{sub 2}Li) and Li{sub 2}CO{sub 3} were found in addition to the above-mentioned compounds. Decomposition of lithium alkyl carbonates to Li{sub 2}CO{sub 3} occurred on negative electrodes stored at elevated temperature. Initial depth-profiling results suggest that the surface layer thickness is greater on positive electrode samples from cells stored at high temperature than on samples from cells stored at room temperature. This observation is significant because positive electrode impedance, and more specifically, charge-transfer resistance at the electrode/electrolyte interface, has been shown to be the main contributor to impedance rise in these cells.

  6. Surface acoustic wave generation and detection using graphene interdigitated transducers on lithium niobate

    SciTech Connect

    Mayorov, A. S.; Hunter, N.; Muchenje, W.; Wood, C. D.; Rosamond, M.; Linfield, E. H.; Davies, A. G.; Cunningham, J. E.

    2014-02-24

    We demonstrate the feasibility of using graphene as a conductive electrode for the generation and detection of surface acoustic waves at 100 s of MHz on a lithium niobate substrate. The graphene interdigitated transducers (IDTs) show sensitivity to doping and temperature, and the characteristics of the IDTs are discussed in the context of a lossy transmission line model.

  7. In situ neutron radiography of lithium-ion batteries: the gas evolution on graphite electrodes during the charging

    NASA Astrophysics Data System (ADS)

    Goers, D.; Holzapfel, M.; Scheifele, W.; Lehmann, E.; Vontobel, P.; Novák, P.

    In situ neutron radiography (NR) was used to study the gas evolution on graphite electrodes in lithium-ion cells containing different PVDF-based gel-type electrolytes. The amount of gas bubbles and channels was calculated by image analysis. Gas production was extremely high in the case of the electrolyte containing ethylene carbonate (EC) and propylene carbonate (PC) (2:3, w/w), 1 M LiClO 4. About 60% of the electrode surface consisted of the gas phase which resulted in an inhomogeneous local current distribution. In contrast, the electrolyte containing EC and γ-butyrolactone (GBL) (1:1, w/w), 1 M LiBF 4 only showed a small increase of the gas volume between the electrodes of about 3%. In situ NR also revealed the displacement of the electrolyte due to gas evolution and volume changes of the electrodes.

  8. Lithium Batteries: Carbon-Rich Active Materials with Macrocyclic Nanochannels for High-Capacity Negative Electrodes in All-Solid-State Lithium Rechargeable Batteries (Small 25/2016).

    PubMed

    Sato, Sota; Unemoto, Atsushi; Ikeda, Takuji; Orimo, Shin-Ichi; Isobe, Hiroyuki

    2016-07-01

    On page 3381, S. Sato, S. Orimo, H. Isobe, and co-workers present the first macrocyclic material to be utilized in negative electrodes of all-solid-state, rechargeable lithium batteries. Assembled to align the molecular openings, the macrocycle paves paths for lithium to migrate to the π-stack intercalation sites for the storage. The macrocyclic nanochannel of a nanometer-scale diameter further provides extra spaces for the lithium storage to surpass conventional graphitic electrodes in the capacity. PMID:27364310

  9. The lithium ion capacitor with a negative electrode of lithium titanium zirconium phosphate

    NASA Astrophysics Data System (ADS)

    Peng, Chien-Ju; Tsai, Dah-Shyang; Chang, Chuan-hua; Wei, Hao-Yu

    2015-01-01

    Nanoparticles of LiTi1.5Zr0.5(PO4)3 (LT1.5Z0.5P) with a nasicon-type structure have been prepared through a sol-gel modified pechini method, which allows a low synthesis temperature and yields a small crystallite size of 36 nm. When implemented as the negative electrode in a hybrid capacitor, LT1.5Z0.5P exhibits a sizable lithium capacity of 6-4 mol below 2.0 V vs. Li/Li+. But the actual capacity being exploited depends on the position of open circuit potential (OCP) at 0% state of charge (SOC). For the capacitor with a 1:1 mass ratio of LT1.5Z0.5P over activated carbon (AC), OCP at 0% SOC generally decreases with increasing mass-specific current and voltage window size, varying between 2.0 and 1.5 V vs. Li/Li+. Hence the LT1.5Z0.5P electrode surpasses the AC electrode in capacitance at high currents, leading to the LT1.5Z0.5P/AC capacitor behaves similar to a double layer capacitor. Conversely, the LT1.5Z0.5P/AC capacitor exhibits more battery-like traits at low specific currents. The maximum energy density of this hybrid cell measures 46.7 Wh kg-1 at voltage window 3.4 V and specific current 70 mA g-1.

  10. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

    PubMed

    Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

    2013-05-21

    Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

  11. Mechanism of Silicon Electrode Aging upon Cycling in Full Lithium-Ion Batteries.

    PubMed

    Delpuech, Nathalie; Dupre, Nicolas; Moreau, Philippe; Bridel, Jean-Sebastian; Gaubicher, Joel; Lestriez, Bernard; Guyomard, Dominique

    2016-04-21

    Understanding the aging mechanism of silicon-based negative electrodes for lithium-ion batteries upon cycling is essential to solve the problem of low coulombic efficiency and capacity fading and further to implement this new high-capacity material in commercial cells. Nevertheless, such studies have so far focused on half cells in which silicon is cycled versus an infinite reservoir of lithium. In the present work, the aging mechanism of silicon-based electrodes is studied upon cycling in a full Li-ion cell configuration with LiCoO2 as the positive electrode. Postmortem analyses of both electrodes clearly indicate that neither one of them contains lithium and that no discernible degradation results from the cycling. The aging mechanism can be explained by the reduction of solvent molecules. Electrons extracted from the positive electrode are responsible for an internal imbalance in the cell, which results in progressive slippage of the electrodes and reduces the compositional range of cyclable lithium ions for both electrodes. PMID:26915951

  12. Stabilizing the surface of lithium metal

    SciTech Connect

    Vaughey, J. T.; Liu, Gao; Zhang, Ji-Guang

    2014-05-01

    Lithium metal is an ideal anode for the next generation of high capacity rechargeable batteries, including Li-air, Li-S, and other Li-based batteries using intercalation compounds. To enable the broad applications for lithium anodes, more fundamental studies need to be conducted to simultaneously address the two barriers discussed above. One of the key breakthroughs in this field may come from the development of new electrolytes (and additives) which can form a stable SEI layer with enough mechanical strength and flexibility. The ideal electrolyte may consist of only two components; one component inhibits dendrite growth, while another component forms a stable SEI layer to improve Coulombic efficiency. In this review, the status of three approaches at manipulating and controlling the lithium metal – electrolyte interface were discussed. While previous studies concentrated on coatings with minimal surface connectivity, the approaches discussed, namely a coating that forms and dissipates into the electrolyte based on charge density, a coating bonded to the termination layer of lithium, and a conformal carbonate coating formed at the interface, all highlight new research directions. Although there are still many obstacles to be overcome, we are optimistic that Li metal can be used as an anode in rechargeable batteries in the foreseeable future. This will enable wide

  13. Fabrication methods for low impedance lithium polymer electrodes

    DOEpatents

    Chern, Terry Song-Hsing; MacFadden, Kenneth Orville; Johnson, Steven Lloyd

    1997-01-01

    A process for fabricating an electrolyte-electrode composite suitable for high energy alkali metal battery that includes mixing composite electrode materials with excess liquid, such as ethylene carbonate or propylene carbonate, to produce an initial formulation, and forming a shaped electrode therefrom. The excess liquid is then removed from the electrode to compact the electrode composite which can be further compacted by compression. The resulting electrode exhibits at least a 75% lower resistance.

  14. Fabrication methods for low impedance lithium polymer electrodes

    DOEpatents

    Chern, T.S.; MacFadden, K.O.; Johnson, S.L.

    1997-12-16

    A process is described for fabricating an electrolyte-electrode composite suitable for high energy alkali metal battery that includes mixing composite electrode materials with excess liquid, such as ethylene carbonate or propylene carbonate, to produce an initial formulation, and forming a shaped electrode therefrom. The excess liquid is then removed from the electrode to compact the electrode composite which can be further compacted by compression. The resulting electrode exhibits at least a 75% lower resistance.

  15. Three-dimensional silicon/carbon core-shell electrode as an anode material for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Jung Sub; Pfleging, Wilhelm; Kohler, Robert; Seifert, Hans Jürgen; Kim, Tae Yong; Byun, Dongjin; Jung, Hun-Gi; Choi, Wonchang; Lee, Joong Kee

    2015-04-01

    Practical application of silicon anodes for lithium-ion batteries has been mainly hindered because of their low electrical conductivity and large volume change (ca. 300%) occurring during the lithiation and delithiation processes. Thus, the surface engineering of active particles (material design) and the modification of electrode structure (electrode design) of silicon are necessary to alleviate these critical limiting factors. Silicon/carbon core-shell particles (Si@C, material design) are prepared by the thermal decomposition and subsequent three-dimensional (3D) electrode structures (electrode design) with a channel width of 15 μm are incorporated using the laser ablation process. The electrochemical characteristics of 3D Si@C used as the anode material for lithium-ion batteries are investigated to identify the effects of material and electrode design. By the introduction of a carbon coating and the laser structuring, an enhanced performance of Si anode materials exhibiting high specific capacity (>1200 mAh g-1 over 300 cycles), good rate capability (1170 mAh g-1 at 8 A g-1), and stable cycling is achieved. The morphology of the core-shell active material combined with 3D channel architecture can minimize the volume expansion by utilizing the void space during the repeated cycling.

  16. Effect of Phosphorus-Doping on Electrochemical Performance of Silicon Negative Electrodes in Lithium-Ion Batteries.

    PubMed

    Domi, Yasuhiro; Usui, Hiroyuki; Shimizu, Masahiro; Kakimoto, Yuta; Sakaguchi, Hiroki

    2016-03-23

    The effect of phosphorus (P)-doping on the electrochemical performance of Si negative electrodes in lithium-ion batteries was investigated. Field-emission scanning electron microscopy was used to observe changes in surface morphology. Surface crystallinity and the phase transition of Si negative electrodes before and after a charge-discharge cycle were investigated by Raman spectroscopy and X-ray diffraction. Li insertion energy into Si was also calculated based on computational chemistry. The results showed that a low P concentration of 124 ppm has a meaningful influence on the electrochemical properties of a Si negative electrode; the cycle performance is improved by P-doping of Si. P-doping suppresses the changes in the surface morphology of a Si negative electrode and the phase transition during a charge-discharge cycle. Li insertion energy increases with an increase in the P concentration; Li insertion into P-doped Si is energetically unfavorable, which indicates that the crystal lattice of Si shrinks as a result of the replacement of some Si atoms with smaller P atoms, and therefore, it is more difficult to insert Li into P-doped Si. These results reveal that suppression of the phase transition reduces the large change in the volume of Si and prevents a Si negative electrode from disintegrating, which helps to improve the otherwise poor cycle performance of a Si electrode. PMID:26938119

  17. Li-Rich Li-Si Alloy As A Lithium-Containing Negative Electrode Material Towards High Energy Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Iwamura, Shinichiroh; Nishihara, Hirotomo; Ono, Yoshitaka; Morito, Haruhiko; Yamane, Hisanori; Nara, Hiroki; Osaka, Tetsuya; Kyotani, Takashi

    2015-01-01

    Lithium-ion batteries (LIBs) are generally constructed by lithium-including positive electrode materials, such as LiCoO2, and lithium-free negative electrode materials, such as graphite. Recently, lithium-free positive electrode materials, such as sulfur, are gathering great attention from their very high capacities, thereby significantly increasing the energy density of LIBs. Though the lithium-free materials need to be combined with lithium-containing negative electrode materials, the latter has not been well developed yet. In this work, the feasibility of Li-rich Li-Si alloy is examined as a lithium-containing negative electrode material. Li-rich Li-Si alloy is prepared by the melt-solidification of Li and Si metals with the composition of Li21Si5. By repeating delithiation/lithiation cycles, Li-Si particles turn into porous structure, whereas the original particle size remains unchanged. Since Li-Si is free from severe constriction/expansion upon delithiation/lithiation, it shows much better cyclability than Si. The feasibility of the Li-Si alloy is further examined by constructing a full-cell together with a lithium-free positive electrode. Though Li-Si alloy is too active to be mixed with binder polymers, the coating with carbon-black powder by physical mixing is found to prevent the undesirable reactions of Li-Si alloy with binder polymers, and thus enables the construction of a more practical electrochemical cell.

  18. Li-rich Li-Si alloy as a lithium-containing negative electrode material towards high energy lithium-ion batteries.

    PubMed

    Iwamura, Shinichiroh; Nishihara, Hirotomo; Ono, Yoshitaka; Morito, Haruhiko; Yamane, Hisanori; Nara, Hiroki; Osaka, Tetsuya; Kyotani, Takashi

    2015-01-01

    Lithium-ion batteries (LIBs) are generally constructed by lithium-including positive electrode materials, such as LiCoO2, and lithium-free negative electrode materials, such as graphite. Recently, lithium-free positive electrode materials, such as sulfur, are gathering great attention from their very high capacities, thereby significantly increasing the energy density of LIBs. Though the lithium-free materials need to be combined with lithium-containing negative electrode materials, the latter has not been well developed yet. In this work, the feasibility of Li-rich Li-Si alloy is examined as a lithium-containing negative electrode material. Li-rich Li-Si alloy is prepared by the melt-solidification of Li and Si metals with the composition of Li21Si5. By repeating delithiation/lithiation cycles, Li-Si particles turn into porous structure, whereas the original particle size remains unchanged. Since Li-Si is free from severe constriction/expansion upon delithiation/lithiation, it shows much better cyclability than Si. The feasibility of the Li-Si alloy is further examined by constructing a full-cell together with a lithium-free positive electrode. Though Li-Si alloy is too active to be mixed with binder polymers, the coating with carbon-black powder by physical mixing is found to prevent the undesirable reactions of Li-Si alloy with binder polymers, and thus enables the construction of a more practical electrochemical cell. PMID:25626879

  19. Li-Rich Li-Si Alloy As A Lithium-Containing Negative Electrode Material Towards High Energy Lithium-Ion Batteries

    PubMed Central

    Iwamura, Shinichiroh; Nishihara, Hirotomo; Ono, Yoshitaka; Morito, Haruhiko; Yamane, Hisanori; Nara, Hiroki; Osaka, Tetsuya; Kyotani, Takashi

    2015-01-01

    Lithium-ion batteries (LIBs) are generally constructed by lithium-including positive electrode materials, such as LiCoO2, and lithium-free negative electrode materials, such as graphite. Recently, lithium-free positive electrode materials, such as sulfur, are gathering great attention from their very high capacities, thereby significantly increasing the energy density of LIBs. Though the lithium-free materials need to be combined with lithium-containing negative electrode materials, the latter has not been well developed yet. In this work, the feasibility of Li-rich Li-Si alloy is examined as a lithium-containing negative electrode material. Li-rich Li-Si alloy is prepared by the melt-solidification of Li and Si metals with the composition of Li21Si5. By repeating delithiation/lithiation cycles, Li-Si particles turn into porous structure, whereas the original particle size remains unchanged. Since Li-Si is free from severe constriction/expansion upon delithiation/lithiation, it shows much better cyclability than Si. The feasibility of the Li-Si alloy is further examined by constructing a full-cell together with a lithium-free positive electrode. Though Li-Si alloy is too active to be mixed with binder polymers, the coating with carbon-black powder by physical mixing is found to prevent the undesirable reactions of Li-Si alloy with binder polymers, and thus enables the construction of a more practical electrochemical cell. PMID:25626879

  20. Mesoporous Li4Ti5O12 nanoclusters as high performance negative electrodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sun, Li; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan

    2014-02-01

    Porous Li4Ti5O12 nanoclusters with high surface area are synthesized by a facile solution-based method followed by low-temperature calcination. The Li4Ti5O12 nanoclusters present the key characteristics needed to serve as high-performance negative electrodes for lithium ion batteries, including nano-sized dimension of the Li4Ti5O12 clusters (50-100 nm) for short ion and electron transfer path, and high surface area (142 m2 g-1) with mesoporosity (pore diameter 2-6 nm) for easy access to the electrolyte and efficient ion transport. Based on these characteristics, the Li4Ti5O12 electrode delivers an initial capacity of 173 mAh g-1 at the rate of 0.5 C, comparable to its theoretical capacity. Excellent cycling stability at high rates is achieved in the Li4Ti5O12 electrode, offering potential to serve as a negative electrode material for high rate lithium ion battery applications.

  1. Method of preparing an electrode material of lithium-aluminum alloy

    DOEpatents

    Settle, Jack L.; Myles, Kevin M.; Battles, James E.

    1976-01-01

    A solid compact having a uniform alloy composition of lithium and aluminum is prepared as a negative electrode for an electrochemical cell. Lithium losses during preparation are minimized by dissolving aluminum within a lithium-rich melt at temperatures near the liquidus temperatures. The desired alloy composition is then solidified and fragmented. The fragments are homogenized to a uniform composition by annealing at a temperature near the solidus temperature. After comminuting to fine particles, the alloy material can be blended with powdered electrolyte and pressed into a solid compact having the desired electrode shape. In the preparation of some electrodes, an electrically conductive metal mesh is embedded into the compact as a current collector.

  2. Olivine electrode engineering impact on the electrochemical performance of lithium-ion batteries.

    SciTech Connect

    Lu, W.; Jansen, A.; Dees, D.; Henriksen, G.; Chemical Sciences and Engineering Division

    2010-08-01

    High energy and power density lithium iron phosphate was studied for hybrid electric vehicle applications. This work addresses the effects of porosity in a composite electrode using a four-point probe resistivity analyzer, galvanostatic cycling, and electrochemical impedance spectroscopy (EIS). The four-point probe result indicates that the porosity of composite electrode affects the electronic conductivity significantly. This effect is also observed from the cell's pulse current discharge performance. Compared to the direct current (dc) methods used, the EIS data are more sensitive to electrode porosity, especially for electrodes with low porosity values.

  3. R&D on lithium batteries in the USA: high-energy electrode materials

    NASA Astrophysics Data System (ADS)

    Owens, Boone B.; Smyrl, William H.; Xu, Jun John

    Recent trends in R&D on lithium battery technology in the USA continue to focus on high-performance batteries, polymer electrolyte systems and the development and production of batteries for specialty markets. Research on sol-gel derived amorphous vanadium and manganese oxides as high capacity, high-energy electrode materials has shown these morphologies are capable of reversibly intercalating very large amounts of lithium and they are attractive cathode candidates. Methods to improve the kinetics of these positive electrodes are showing promise.

  4. Cu2Sb thin film electrodes prepared by pulsed laser deposition f or lithium batteries

    SciTech Connect

    Song, Seung-Wan; Reade, Ronald P.; Cairns, Elton J.; Vaughey, Jack T.; Thackeray, Michael M.; Striebel, Kathryn A.

    2003-08-01

    Thin films of Cu2Sb, prepared on stainless steel and copper substrates with a pulsed laser deposition technique at room temperature, have been evaluated as electrodes in lithium cells. The electrodes operate by a lithium insertion/copper extrusion reaction mechanism, the reversibility of which is superior when copper substrates are used, particularly when electrochemical cycling is restricted to the voltage range 0.65-1.4 V vs. Li/Li+. The superior performance of Cu2Sb films on copper is attributed to the more active participation of the extruded copper in the functioning of the electrode. The continual and extensive extrusion of copper on cycling the cells leads to the isolation of Li3Sb particles and a consequent formation of Sb. Improved cycling stability of both types of electrodes was obtained when cells were cycled between 0.65 and 1.4 V. A low-capacity lithium-ion cell with Cu2Sb and LiNi0.8Co0.15Al0.05O2 electrodes, laminated from powders, shows excellent cycling stability over the voltage range 3.15 - 2.2 V, the potential difference corresponding to approximately 0.65-1.4 V for the Cu2Sb electrode vs. Li/Li+. Chemical self-discharge of lithiated Cu2Sb electrodes by reaction with the electrolyte was severe when cells were allowed to relax on open circuit after reaching a lower voltage limit of 0.1 V. The solid electrolyte interphase (SEI) layer formed on Cu2Sb electrodes after cells had been cycled between 1.4 and 0.65 V vs. Li/Li+ was characterized by Fourier-transform infrared spectroscopy; the SEI layer contributes to the large irreversible capacity loss on the initial cycle of these cells. The data contribute to a better understanding of the electrochemical behavior of intermetallic electrodes in rechargeable lithium batteries.

  5. Mapping the anode surface-electrolyte interphase: investigating a life limiting process of lithium primary batteries.

    PubMed

    Bock, David C; Tappero, Ryan V; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

    2015-03-11

    Cathode solubility in batteries can lead to decreased and unpredictable long-term battery behavior due to transition metal deposition on the negative electrode such that it no longer supports high current. Analysis of negative electrodes from cells containing vanadium oxide or phosphorus oxide based cathode systems retrieved after long-term testing was conducted. This report demonstrates the use of synchrotron based X-ray microfluorescence (XRμF) to map negative battery electrodes in conjunction with microbeam X-ray absorption spectroscopy (μXAS) to determine the oxidation states of the metal centers resident in the solid electrolyte interphase (SEI) and at the electrode surface. Based on the empirical findings, a conceptual model for the location of metal ions in the SEI and their role in impacting lithium ion mobility at the electrode surfaces is proposed. PMID:25690846

  6. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

    PubMed

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

  7. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

    NASA Astrophysics Data System (ADS)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-04-01

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

  8. Understanding the Degredation of Silicion Electrodes for Lithium Ion Batteries Using Acoustic Emission

    SciTech Connect

    Rhodes, Kevin J; Dudney, Nancy J; Lara-Curzio, Edgar; Daniel, Claus

    2010-01-01

    Silicon is a promising anode material for lithium ion battery application due to its high specific capacity, low cost, and abundance. However, when silicon is lithiated at room temperature it can undergo a volume expansion in excess of 280% which leads to extensive fracturing. This is thought to be a primary cause of the rapid decay in cell capacity routinely observed. Acoustic emission (AE) was employed to monitor activity in composite silicon electrodes while cycling in lithium ion half-cells using a constant current-constant voltage procedure. The major source of AE was identified as the brittle fracture of silicon particles resulting from the alloying reaction that gives rise to LixSi phases. The largest number of emissions occurred on the first lithiation corresponding to surface fracture of the silicon particles, followed by distinct emission bursts on subsequent charge and discharge steps. Furthermore, a difference in the average parameters describing emission during charge and discharge steps was observed. Potential diagnostic and materials development applications of the presented AE techniques are discussed.

  9. Rechargeable aqueous lithium-air batteries with an auxiliary electrode for the oxygen evolution

    NASA Astrophysics Data System (ADS)

    Sunahiro, S.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

    2014-09-01

    A rechargeable aqueous lithium-air cell with a third auxiliary electrode for the oxygen evolution reaction was developed. The cell consists of a lithium metal anode, a lithium conducting solid electrolyte of Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12, a carbon black oxygen reduction air electrode, a RuO2 oxygen evolution electrode, and a saturated aqueous solution of LiOH with 10 M LiCl. The cell was successfully operated for several cycles at 0.64 mA cm-2 and 25 °C under air, where the capacity of air electrode was 2000 mAh gcathod-1. The cell performance was degraded gradually by cycling under open air. The degradation was reduced under CO2-free air and pure oxygen. The specific energy density was calculated to be 810 Wh kg-1 from the weight of water, lithium, oxygen, and carbon in the air electrode.

  10. Lithium sulfide compositions for battery electrolyte and battery electrode coatings

    DOEpatents

    Liang, Chengdu; Liu, Zengcai; Fu, Wunjun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

    2013-12-03

    Methods of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electroytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one or .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

  11. Lithium sulfide compositions for battery electrolyte and battery electrode coatings

    DOEpatents

    Liang, Chengdu; Liu, Zengcai; Fu, Wujun; Lin, Zhan; Dudney, Nancy J; Howe, Jane Y; Rondinone, Adam J

    2014-10-28

    Method of forming lithium-containing electrolytes are provided using wet chemical synthesis. In some examples, the lithium containing electrolytes are composed of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7. The solid electrolyte may be a core shell material. In one embodiment, the core shell material includes a core of lithium sulfide (Li.sub.2S), a first shell of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7, and a second shell including one of .beta.-Li.sub.3PS.sub.4 or Li.sub.4P.sub.2S.sub.7 and carbon. The lithium containing electrolytes may be incorporated into wet cell batteries or solid state batteries.

  12. Carbon nanotube/Co3O4 composite for air electrode of lithium-air battery

    NASA Astrophysics Data System (ADS)

    Yoon, Taek Han; Park, Yong Joon

    2012-01-01

    A carbon nanotube [CNT]/Co3O4 composite is introduced as a catalyst for the air electrode of lithium-air [Li/air] batteries. Co3O4 nanoparticles are successfully attached to the sidewall of the CNT by a hydrothermal method. A high discharge capacity and a low overvoltage indicate that the CNT/Co3O4 composite is a very promising catalyst for the air electrode of Li/air batteries.

  13. Infiltrated Porous Polymer Sheets as Free-Standing Flexible Lithium-Sulfur Battery Electrodes.

    PubMed

    Wu, Feixiang; Zhao, Enbo; Gordon, Daniel; Xiao, Yiran; Hu, Chenchen; Yushin, Gleb

    2016-08-01

    Free-standing, high-capacity Li2 S electrodes with capacity loadings in the range from 1.5 to 3.8 mA h cm(-2) are produced by using infiltration of active materials into porous carbonized biomass sheets. The proposed electrode design can be effectively utilized for the low-cost fabrication of flexible lithium batteries with high specific energy. PMID:27168478

  14. Carbon nanotube/Co3O4 composite for air electrode of lithium-air battery

    PubMed Central

    2012-01-01

    A carbon nanotube [CNT]/Co3O4 composite is introduced as a catalyst for the air electrode of lithium-air [Li/air] batteries. Co3O4 nanoparticles are successfully attached to the sidewall of the CNT by a hydrothermal method. A high discharge capacity and a low overvoltage indicate that the CNT/Co3O4 composite is a very promising catalyst for the air electrode of Li/air batteries. PMID:22222030

  15. Carbon nanotube/Co3O4 composite for air electrode of lithium-air battery.

    PubMed

    Yoon, Taek Han; Park, Yong Joon

    2012-01-01

    A carbon nanotube [CNT]/Co3O4 composite is introduced as a catalyst for the air electrode of lithium-air [Li/air] batteries. Co3O4 nanoparticles are successfully attached to the sidewall of the CNT by a hydrothermal method. A high discharge capacity and a low overvoltage indicate that the CNT/Co3O4 composite is a very promising catalyst for the air electrode of Li/air batteries. PMID:22222030

  16. Lithium-ion capacitors with 2D Nb2CTx (MXene) - carbon nanotube electrodes

    NASA Astrophysics Data System (ADS)

    Byeon, Ayeong; Glushenkov, Alexey M.; Anasori, Babak; Urbankowski, Patrick; Li, Jingwen; Byles, Bryan W.; Blake, Brian; Van Aken, Katherine L.; Kota, Sankalp; Pomerantseva, Ekaterina; Lee, Jae W.; Chen, Ying; Gogotsi, Yury

    2016-09-01

    There is a growing interest to hybrid energy storage devices, such as lithium-ion capacitors, in which battery-type electrodes are combined with capacitor-type ones. It is anticipated that the energy density (either gravimetric or volumetric) of lithium-ion capacitors is improved if pseudocapacitive or fast insertion materials are used instead of conventional activated carbon (AC) in the capacitor-type electrode. MXenes, a new family of two-dimensional transition metal carbides, demonstrate metallic conductivity and fast charge-discharge behavior that make them suitable for this application. In this study, we move beyond single electrodes, half-cell studies and demonstrate three types of hybrid cells using Nb2CTx-carbon nanotube (CNT) films. It is shown that lithiated graphite/Nb2CTx-CNT, Nb2CTx-CNT/LiFePO4 and lithiated Nb2CTx-CNT/Nb2CTx-CNT cells are all able to operate within 3 V voltage windows and deliver capacities of 43, 24 and 36 mAh/g (per total weight of two electrodes), respectively. Moreover, the polarity of the electrodes can be reversed in the symmetric Nb2CTx-CNT cells from providing a positive potential between 0 and 3 V to a negative one from -3 to 0 V. It is shown that the volumetric energy density (50-70 Wh/L) of our first-generation devices with MXene electrodes exceeds that of a lithium titanate/AC capacitor.

  17. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  18. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  19. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  20. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  1. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  2. Intermetallic negative electrodes for non-aqueous lithium cells and batteries

    DOEpatents

    Thackeray, Michael M.; Vaughey, John T.; Johnson, Christopher S.; Fransson, Linda M.; Edstrom, Ester Kristina; Henriksen, Gary

    2004-05-04

    A method of operating an electrochemical cell is disclosed. The cell has an intermetallic negative electrode of Cu.sub.6-x M.sub.x Sn.sub.5, wherein x is .ltoreq.3 and M is one or more metals including Si and a positive electrode containing Li in which Li is shuttled between the positive electrode and the negative electrode during charge and discharge to form a lithiated intermetallic negative electrode during charge. The voltage of the electrochemical cell is controlled during the charge portion of the charge-discharge cycles so that the potential of the lithiated intermetallic negative electrode in the fully charged electrochemical cell is less than 0.2 V but greater than 0 V versus metallic lithium.

  3. Electrolytic method for the production of lithium using a lithium-amalgam electrode

    DOEpatents

    Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

    1979-01-01

    A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

  4. Advanced Materials for Neural Surface Electrodes

    PubMed Central

    Schendel, Amelia A.; Eliceiri, Kevin W.; Williams, Justin C.

    2015-01-01

    Designing electrodes for neural interfacing applications requires deep consideration of a multitude of materials factors. These factors include, but are not limited to, the stiffness, biocompatibility, biostability, dielectric, and conductivity properties of the materials involved. The combination of materials properties chosen not only determines the ability of the device to perform its intended function, but also the extent to which the body reacts to the presence of the device after implantation. Advances in the field of materials science continue to yield new and improved materials with properties well-suited for neural applications. Although many of these materials have been well-established for non-biological applications, their use in medical devices is still relatively novel. The intention of this review is to outline new material advances for neural electrode arrays, in particular those that interface with the surface of the nervous tissue, as well as to propose future directions for neural surface electrode development. PMID:26392802

  5. Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes.

    PubMed

    Shon, Jeong Kuk; Lee, Hyo Sug; Park, Gwi Ok; Yoon, Jeongbae; Park, Eunjun; Park, Gyeong Su; Kong, Soo Sung; Jin, Mingshi; Choi, Jae-Man; Chang, Hyuk; Doo, Seokgwang; Kim, Ji Man; Yoon, Won-Sub; Pak, Chanho; Kim, Hansu; Stucky, Galen D

    2016-01-01

    Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g(-1) for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems. PMID:27001935

  6. Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes

    PubMed Central

    Shon, Jeong Kuk; Lee, Hyo Sug; Park, Gwi Ok; Yoon, Jeongbae; Park, Eunjun; Park, Gyeong Su; Kong, Soo Sung; Jin, Mingshi; Choi, Jae-Man; Chang, Hyuk; Doo, Seokgwang; Kim, Ji Man; Yoon, Won-Sub; Pak, Chanho; Kim, Hansu; Stucky, Galen D.

    2016-01-01

    Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g−1 for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems. PMID:27001935

  7. Mechanical stresses and crystallization of lithium phosphorous oxynitride-coated germanium electrodes during lithiation and delithiation

    NASA Astrophysics Data System (ADS)

    Al-Obeidi, Ahmed; Kramer, Dominik; Mönig, Reiner; Thompson, Carl V.

    2016-02-01

    The evolution of mechanical stresses during the cycling of lithium phosphorous oxynitride (LiPON) coated germanium thin film electrodes was monitored using substrate curvature measurements. By coating germanium thin films with LiPON, morphology evolution, e.g. crack and island formation, can be strongly suppressed. LiPON-coated germanium thin film electrodes can retain their planar form during cycling, resulting in a clear and reproducible stress response originating primarily from the electrochemical processes occurring during lithiation and delithiation. Together with the electrochemical data, stress measurements were used to infer mechanisms underlying the alloying of lithium with germanium. The stress signatures associated with individual phases, crystallization, and amorphization of lithium-germanium alloys are reported and discussed.

  8. Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes

    NASA Astrophysics Data System (ADS)

    Shon, Jeong Kuk; Lee, Hyo Sug; Park, Gwi Ok; Yoon, Jeongbae; Park, Eunjun; Park, Gyeong Su; Kong, Soo Sung; Jin, Mingshi; Choi, Jae-Man; Chang, Hyuk; Doo, Seokgwang; Kim, Ji Man; Yoon, Won-Sub; Pak, Chanho; Kim, Hansu; Stucky, Galen D.

    2016-03-01

    Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g-1 for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems.

  9. Surface-enhanced Raman microspectroscopy at electrode surfaces

    SciTech Connect

    Hembree D.M. Jr.; Oswald, J.C.; Smyrl, N.R.

    1987-02-01

    Surface-enhanced Raman microspectroscopy has been developed as a technique for characterizing processes occurring at the electrode/electrolyte interface. A spectroelectrochemical cell was designed to obtain Raman spectra of electrochemical species with the use of microscope optics, which allowed unambiguous placement of laser focus at the electrode surface with spatial resolution on the order of 1 ..mu..m. It was also possible to visually inspect the surface morphology of the electrode with the use of the Raman microscope in the reflected-light mode. The capabilities of the spectroelectrochemical cell were demonstrated by observation of surface-enhanced Raman scattering (SERS) for a variety of model systems (pyridine, pyridinium ion, potassium cyanide) with the use of silver, copper, and nickel electrodes. The electrochemical behavior of a commercially important gold electroplating process is also reported.

  10. Effect of lithium-ion diffusibility on interfacial resistance of LiCoO2 thin film electrode modified with lithium tungsten oxides

    NASA Astrophysics Data System (ADS)

    Hayashi, Tetsutaro; Miyazaki, Takamichi; Matsuda, Yasutaka; Kuwata, Naoaki; Saruwatari, Motoaki; Furuichi, Yuki; Kurihara, Koji; Kuzuo, Ryuichi; Kawamura, Junichi

    2016-02-01

    To investigate the contribution of lithium-ion diffusibility of lithium tungsten oxides (LWOs) to low interfacial resistance, we fabricate thin-film electrodes of 6Li-enriched LiCoO2 (6LCO) modified with various structure-types of 6Li-enriched LWOs by pulsed laser deposition. The electrodes are subjected to X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and secondary-ion mass spectrometry (SIMS) analyses. XRD reveals that the LWO layers have Li2WO4 structure with rhombohedral and tetragonal symmetries and amorphous states. EIS shows that the lowest interfacial resistance of the positive electrodes is given by the amorphous state, followed in order by the tetragonal and the rhombohedral symmetry, and that the diffusion coefficients of lithium-ions in the electrodes increase in the same order. SIMS demonstrates that the fastest lithium-ion self-diffusibility into the LWOs is found in the amorphous state, followed in order by tetragonal and rhombohedral symmetry. Furthermore, the amorphous state LWO modification shows smooth lithium-ion diffusion between the LWO and LCO layers after the electrochemical test. Conversely, the rhombohedral LWO modification demonstrates congested lithium-ion diffusion between the LWO and LCO layers after the test. Thus, fast lithium-ion self-diffusibility into the LWO-modified LCO contributes to enhancing the diffusion of lithium-ions, resulting in the reduction of interfacial resistance.

  11. Investigation of electrolyte wetting in lithium ion batteries: Effects of electrode pore structures and solution

    NASA Astrophysics Data System (ADS)

    Sheng, Yangping

    Beside natural source energy carriers such as petroleum, coal and natural gas, the lithium ion battery is a promising man-made energy carrier for the future. This is a similar process evolved from horse-powered era to engine driven age. There are still a lot of challenges ahead like low energy density, low rate performance, aging problems, high cost and safety etc. In lithium ion batteries, investigation about manufacturing process is as important as the development of material. The manufacturing of lithium ion battery, including production process (slurry making, coating, drying etc.), and post-production (slitting, calendering etc.) is also complicated and critical to the overall performance of the battery. It includes matching the capacity of anode and cathode materials, trial-and-error investigation of thickness, porosity, active material and additive loading, detailed microscopic models to understand, optimize, and design these systems by changing one or a few parameters at a time. In the manufacturing, one of the most important principles is to ensure good wetting properties between porous solid electrodes and liquid electrolyte. Besides the material surface properties, it is the process of electrolyte transporting to fill the pores in the electrode after injection is less noticed in academic, where only 2-3 drops of electrolyte are needed for lab coin cell level. In industry, the importance of electrolyte transport is well known and it is considered as part of electrolyte wetting (or initial wetting in some situations). In consideration of practical usage term, electrolyte wetting is adopted to use in this dissertation for electrolyte transporting process, although the surface chemistry about wetting is not covered. An in-depth investigation about electrolyte wetting is still missing, although it has significant effects in manufacturing. The electrolyte wetting is determined by properties of electrolyte and electrode microstructure. Currently, only viscosity

  12. Oriented nanotube electrodes for lithium ion batteries and supercapacitors

    DOEpatents

    Frank, Arthur J.; Zhu, Kai; Wang, Qing

    2013-03-05

    An electrode having an oriented array of multiple nanotubes is disclosed. Individual nanotubes have a lengthwise inner pore defined by interior tube walls which extends at least partially through the length of the nanotube. The nanotubes of the array may be oriented according to any identifiable pattern. Also disclosed is a device featuring an electrode and methods of fabrication.

  13. Non-aqueous Electrode Processing and Construction of Lithium-ion Coin Cells.

    PubMed

    Stein, Malcolm; Chen, Chien-Fan; Robles, Daniel J; Rhodes, Christopher; Mukherjee, Partha P

    2016-01-01

    Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational analysis. Testing of lithium-ion batteries in an academic setting has taken on several forms, but at the most basic level lies the coin cell construction. In traditional LIB electrode preparation, a multi-phase slurry composed of active material, binder, and conductive additive is cast out onto a substrate. An electrode disc can then be punched from the dried sheet and used in the construction of a coin cell for electrochemical evaluation. Utilization of the potential of the active material in a battery is critically dependent on the microstructure of the electrode, as an appropriate distribution of the primary components are crucial to ensuring optimal electrical conductivity, porosity, and tortuosity, such that electrochemical and transport interaction is optimized. Processing steps ranging from the combination of dry powder, wet mixing, and drying can all critically affect multi-phase interactions that influence the microstructure formation. Electrochemical probing necessitates the construction of electrodes and coin cells with the utmost care and precision. This paper aims at providing a step-by-step guide of non-aqueous electrode processing and coin cell construction for lithium-ion batteries within an academic setting and with emphasis on deciphering the influence of drying and calendaring. PMID:26863503

  14. Optimizing areal capacities through understanding the limitations of lithium-ion electrodes

    SciTech Connect

    Gallagher, Kevin G.; Trask, Stephen E.; Bauer, Christoph; Woehrle, Thomas; Lux, Simon; Tschech, Matthias; Polzin, Bryant J.; Ha, Seungbum; Long, Brandon R.; Wu, Qingliu; Lu, Wenquan; Dees, Dennis W.; Jansen, Andrew N.

    2016-01-01

    Increasing the areal capacity or electrode thickness in lithium ion batteries is one possible means to increase pack level energy density while simultaneously lowering cost. The physics that limit use of high areal capacity as a function of battery power to energy ratio are poorly understood and thus most currently produced automotive lithium ion cells utilize modest loadings to ensure long life over the vehicle battery operation. Here we show electrolyte transport limits the utilization of the positive electrode at critical C-rates during discharge; whereas, a combination of electrolyte transport and polarization lead to lithium plating in the graphite electrode during charge. Experimental measurements are compared with theoretical predictions based on concentrated solution and porous electrode theories. An analytical expression is derived to provide design criteria for long lived operation based on the physical properties of the electrode and electrolyte. Finally, a guideline is proposed that graphite cells should avoid charge current densities near or above 4 mA/cm2 unless additional precautions have been made to avoid deleterious side reaction.

  15. The Science of Electrode Materials for Lithium Batteries - Progress Report

    SciTech Connect

    Brent Fultz

    2003-08-15

    OAK-B135 (IPLD Cleared) Basic materials science research on materials for anodes and cathodes in electrochemical cells. The work is a mix of electrochemical measurements and analysis of the materials by transmission electron microscopy and x-ray diffractometry. The emphasis is on the thermodynamics and kinetics of how lithium is intercalated and de-intercalleted into anode and cathod materials.

  16. Surface microhardening in a lithium implanted aluminium alloy

    SciTech Connect

    Singh, A.; Fiset, M.; Knystautas, E.J.; Lapointe, R.

    1984-09-01

    This paper describes changes observed in microhardness after implanting energetic lithium ions into pure aluminum and its 2024-T351 alloy. The addition of lithium to aluminum lowers the density and increases both the modulus of elasticity and tensile strength. Thus, these properties make such alloys attractive in aerospace applications. The authors believe that this is the first report where lithium implantation has been used to evaluate near surface changes.

  17. Multi-layered, chemically bonded lithium-ion and lithium/air batteries

    SciTech Connect

    Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

    2014-05-13

    Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

  18. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    DOE PAGESBeta

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neithermore » cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.« less

  19. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    SciTech Connect

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neither cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.

  20. One-dimensional nanostructured materials for lithium-ion battery and supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Chan, Candace Kay

    The need for improved electrochemical storage devices has necessitated research on new and advanced electrode materials. One-dimensional nanomaterials such as nanowires, nanotubes, and nanoribbons, can provide a unique opportunity to engineer electrochemical devices to have improved electronic and ionic conductivity as well as electrochemical and structural transformations. Silicon and germanium nanowires (NWs) were studied as negative electrode materials for lithiumion batteries because of their ability to alloy with large amounts of lithium, leading to 4-10 times higher specific capacities than the graphite standard. These nanowires could be grown vertically off of metallic current collector substrates using the gold-catalyzed vapor-liquid-solid synthesis. Electrochemical measurements of the SiNWs showed that capacities greater than 3,500 mAh/g could be obtained for tens of cycles, while hundreds of cycles could be obtained at lower capacities. As opposed to bulk Si, the SiNWs were observed to maintain their morphology during cycling and did not pulverize due to the large volume changes. Detailed TEM and XRD characterization showed that the SiNWs became amorphous during the first lithiation (charge) and formed a two-phase region between crystalline Si and amorphous Li xSi. Afterwards, the SiNWs remained amorphous and subsequent reaction was through a single-phase cycling of amorphous Si. The good cycling behavior compared to bulk and micron-sized Si particles was attributed to the nanowire morphology and electrode design. The surface chemistry and solid-electrolyte interphase (SEI) were studied using XPS as a function of charge and discharge potential. The common reduction productions expected in the electrolyte (1 M LiPF6 in 1:1 EC/DEC) were observed, with the main component being Li2CO3. The morphology of the SEI was found to change at different potentials, indicating a dynamic process involving deposition, dissolution, and re-deposition on the SiNWs. Longterm

  1. Nafion coated sulfur-carbon electrode for high performance lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Tang, Qiwei; Shan, Zhongqiang; Wang, Li; Qin, Xue; Zhu, Kunlei; Tian, Jianhua; Liu, Xuesheng

    2014-01-01

    In this paper, a nafion coated electrode is prepared to improve the performance of lithium sulfur batteries. It is demonstrated from a series of measurements that the nafion layer is quite effective in reducing shuttle effect and enhancing the stability and the reversibility of the electrode. When measured under the rate of 0.2 C, the initial discharge capacity of the nafion coated electrode can reach 1084 mAh g-1, with a Columbic efficiency of about 100%. After 100 charge/discharge cycles, this electrode can also deliver a reversible capacity of as high as 879 mAh g-1. Significantly, the charge-transfer resistance of the electrode tends to be reducing after coated with an appropriate thickness of nafion film. The cation conductivity as well as anion inconductivity is considered to be the dominant factor for the superior electrochemical properties.

  2. Modified lithium vanadium oxide electrode materials products and methods

    DOEpatents

    Thackeray, Michael M.; Kahaian, Arthur J.; Visser, Donald R.; Dees, Dennis W.; Benedek, Roy

    1999-12-21

    A method of improving certain vanadium oxide formulations is presented. The method concerns fluorine doping formulations having a nominal formula of LiV.sub.3 O.sub.8. Preferred average formulations are provided wherein the average oxidation state of the vanadium is at least 4.6. Herein preferred fluorine doped vanadium oxide materials, electrodes using such materials, and batteries including at least one electrode therein comprising such materials are provided.

  3. Investigation of Lithium-Air Battery Discharge Product Formed on Carbon Nanotube and Nanofiber Electrodes

    NASA Astrophysics Data System (ADS)

    Mitchell, Robert Revell, III

    Carbon nanotubes have been actively investigated for integration in a wide variety of applications since their discovery over 20 years ago. Their myriad desirable material properties including exceptional mechanical strength, high thermal conductivities, large surface-to-volume ratios, and considerable electrical conductivities, which are attributable to a quantum mechanical ability to conduct electrons ballistically, have continued to motivate interest in this material system. While a variety of synthesis techniques exist, carbon nanotubes and nanofibers are most often conveniently synthesized using chemical vapor deposition (CVD), which involves their catalyzed growth from transition metal nanoparticles. Vertically-aligned nanotube and nanofiber carpets produced using CVD have been utilized in a variety of applications including those related to energy storage. Li-air (Li-O2) batteries have received much interest recently because of their very high theoretical energy densities (3200 Wh/kgLi2O2 ). which make them ideal candidates for energy storage devices for future fully-electric vehicles. During operation of a Li-air battery O2 is reduced on the surface a porous air cathode, reacting with Li-ions to form lithium peroxide (Li-O2). Unlike the intercalation reactions of Li-ion batteries, discharge in a Li-air cell is analogous to an electrodeposition process involving the nucleation and growth of the depositing species on a foreign substrate. Carbon nanofiber electrodes were synthesized on porous substrates using a chemical vapor deposition process and then assembled into Li-O2 cells. The large surface to volume ratio and low density of carbon nanofiber electrodes were found to yield a very high gravimetric energy density in Li-O 2 cells, approaching 75% of the theoretical energy density for Li 2O2. Further, the carbon nanofiber electrodes were found to be excellent platforms for conducting ex situ electron microscopy investigations of the deposition Li2O2 phase

  4. Liquid surface skimmer apparatus for molten lithium and method

    DOEpatents

    Robinson, Samuel C.; Pollard, Roy E.; Thompson, William F.; Stark, Marshall W.; Currin, Jr., Robert T.

    1995-01-01

    This invention relates to an apparatus for separating two fluids having different specific gravities. The invention also relates to a method for using the separating apparatus of the present invention. This invention particularly relates to the skimming of molten lithium metal from the surface of a fused salt electrolyte in the electrolytic production of lithium metal from a mixed fused salt.

  5. How voltage drops are manifested by lithium ion configurations at interfaces and in thin films on battery electrodes

    SciTech Connect

    Leung, Kevin; Leenheer, Andrew Jay

    2015-04-09

    Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode–surface film interface in response to the voltage, which adds complexity to the “electric double layer” (EDL). We also apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic length scales, including charge separation and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the “lithium cohesive energy”-based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. Furthermore, this distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials.

  6. How voltage drops are manifested by lithium ion configurations at interfaces and in thin films on battery electrodes

    DOE PAGESBeta

    Leung, Kevin; Leenheer, Andrew Jay

    2015-04-09

    Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode–surface film interface in response to the voltage, which adds complexity to the “electric double layer” (EDL). We also apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic length scales, including charge separation and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We proposemore » that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the “lithium cohesive energy”-based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. Furthermore, this distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials.« less

  7. Hierarchically Porous Graphene as a Lithium-Air Battery Electrode

    SciTech Connect

    Xiao, Jie; Mei, Donghai; Li, Xiaolin; Xu, Wu; Wang, Deyu; Graff, Gordon L.; Bennett, Wendy D.; Nie, Zimin; Saraf, Laxmikant V.; Aksay, Ilhan A.; Liu, Jun; Zhang, Jiguang

    2011-11-09

    Functionalized graphene sheets (FGS) are successfully utilized as a novel air electrode for Li-O2 batteries. An extremely high capacity of 15,000 mAh/g was achieved by using the as-prepared graphene air electrode at a current density of 0.1 mA/cm2 in the pure oxygen environment. Although there is no pore in the two-dimensional FGS the as-prepared graphene air electrode consists of randomly arranged graphene nano-sheets which automatically form tunnels with different sizes. The large tunnels work as highways for the oxygen to quickly flow into the air electrode while the small pore-like tunnels can be considered as the numerous exits where the discharge products are accumulated. Combined with an appropriate electrolyte, the ideal discharge product Li2O2 is obtained without any carbonates byproducts in this system. Even when operated in ambient environment with a relative humidity of ~20% the specific capacity delivered from the pouch type cell achieves more than 5000 mAh/g making the graphene-based air electrode extremely attractive in the energy storage applications.

  8. Sandwich electrode designed for high performance lithium-ion battery.

    PubMed

    Zhao, Chunsong; Luo, Xi; Chen, Chengmeng; Wu, Hui

    2016-05-01

    We fabricated a sandwich structure Li-ion battery electrode by trapping micron-sized silicon between a copper current collector and a graphene coating. During dynamic electrochemical cycles, the volume change of the silicon can be buffered by the coating through the deformation of soft graphenes. This structure can effectively prevent the silicon particles from escaping from the current collector while keeping the buffered graphene coating integrated and unbroken during deformation. The electrodes could be maintained for 400 cycles at a constant charge capacity of 1000 mA h g(-1). PMID:27117447

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

    NASA Astrophysics Data System (ADS)

    Yang, Ming-Che

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

  10. The Science of Electrode Materials for Lithium Batteries

    SciTech Connect

    Fultz, Brent

    2007-03-15

    Rechargeable lithium batteries continue to play the central role in power systems for portable electronics, and could play a role of increasing importance for hybrid transportation systems that use either hydrogen or fossil fuels. For example, fuel cells provide a steady supply of power, whereas batteries are superior when bursts of power are needed. The National Research Council recently concluded that for dismounted soldiers "Among all possible energy sources, hybrid systems provide the most versatile solutions for meeting the diverse needs of the Future Force Warrior. The key advantage of hybrid systems is their ability to provide power over varying levels of energy use, by combining two power sources." The relative capacities of batteries versus fuel cells in a hybrid power system will depend on the capabilities of both. In the longer term, improvements in the cost and safety of lithium batteries should lead to a substantial role for electrochemical energy storage subsystems as components in fuel cell or hybrid vehicles. We have completed a basic research program for DOE BES on anode and cathode materials for lithium batteries, extending over 6 years with a 1 year phaseout period. The emphasis was on the thermodynamics and kinetics of the lithiation reaction, and how these pertain to basic electrochemical properties that we measure experimentally — voltage and capacity in particular. In the course of this work we also studied the kinetic processes of capacity fade after cycling, with unusual results for nanostructued Si and Ge materials, and the dynamics underlying electronic and ionic transport in LiFePO4. This document is the final report for this work.

  11. Thermal stability of electrodes in Lithium-ion cells

    SciTech Connect

    ROTH,EMANUEL P.; NAGASUBRAMANIAN,GANESAN

    2000-02-07

    Differential scanning calorimetry (DSC) analysis was used to identify thermal reactions in Sony-type lithium-ion cells and to correlate these reactions with interactions of cell constituents and reaction products. An electrochemical half-cell was used to cycle the anode and cathode materials and to set the state-of-charge (SOC). Three temperature regions of interaction were identified and associated with the SOC (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 80 C involving decomposition of the solid electrolyte interphase (SEI) layer. The LiPF{sub 6} salt in the electrolyte (EC:PC:DEC/1M LiPF{sub 6}) was seen to play an essential role in this reaction. DSC analysis of the anodes from disassembled Sony cells showed similar behavior to the half-cell anodes with a strong exotherm beginning in the 80 C--90 C range. Exothermic reactions were also observed in the 200 C--300 C region between the intercalated lithium anodes, the LiPF{sub 6} salt, and the PVDF binder. These reactions were followed by a high-temperature reaction region, 300 C--400 C, also involving the PVDF binder and the intercalated lithium anodes. Cathode exothermic reactions with the PVDF binder were observed above 200 C and increased with the SOC (decreasing Li content in the cathode). No thermal reactions were seen at lower temperatures suggesting that thermal runaway reactions in this type of cell are initiated at the anode. An Accelerating Rate Calorimeter (ARC) was used to perform measurements of thermal runaway on commercial Sony Li-ion cells as a function of SOC. The cells showed sustained thermal output as low as 80 C in agreement with the DSC observations of anode materials but the heating rate was strongly dependent on the SOC.

  12. A MEMS platform for in situ, real-time monitoring of electrochemically induced mechanical changes in lithium-ion battery electrodes

    NASA Astrophysics Data System (ADS)

    Pomerantseva, Ekaterina; Jung, Hyun; Gnerlich, Markus; Baron, Sergio; Gerasopoulos, Konstantinos; Ghodssi, Reza

    2013-11-01

    We report the first successful demonstration of an optical microelectromechanical systems (MEMS) sensing platform for the in situ characterization of electrochemically induced reversible mechanical changes in lithium-ion battery (LIB) electrodes. The platform consists of an array of flexible membranes with a reflective surface on one side and a thin-film LIB electrode on the other side. The membranes deflect due to the active battery material volume change caused by lithium intercalation (expansion) and extraction (contraction). This deflection is monitored using the Fabry-Perot optical interferometry principle. The active material volume change causes high internal stresses and mechanical degradation of the electrodes. The stress evolution observed in a silicon thin-film electrode incorporated into this MEMS platform follows a ‘first elastic, then plastic’ deformation scheme. Understanding of the internal stresses in battery electrodes during discharge/charge is important for improving the reliability and cycle lifetime of LIBs. The developed MEMS platform presents a new method for in situ diagnostics of thin-film LIB electrodes to aid the development of new materials, optimization of electrode performance, and prevention of battery failure.

  13. Reactivity of carbon in lithium-oxygen battery positive electrodes.

    PubMed

    Itkis, Daniil M; Semenenko, Dmitry A; Kataev, Elmar Yu; Belova, Alina I; Neudachina, Vera S; Sirotina, Anna P; Hävecker, Michael; Teschner, Detre; Knop-Gericke, Axel; Dudin, Pavel; Barinov, Alexei; Goodilin, Eugene A; Shao-Horn, Yang; Yashina, Lada V

    2013-10-01

    Unfortunately, the practical applications of Li-O2 batteries are impeded by poor rechargeability. Here, for the first time we show that superoxide radicals generated at the cathode during discharge react with carbon that contains activated double bonds or aromatics to form epoxy groups and carbonates, which limits the rechargeability of Li-O2 cells. Carbon materials with a low amount of functional groups and defects demonstrate better stability thus keeping the carbon will-o'-the-wisp lit for lithium-air batteries. PMID:24004050

  14. Synthesis and characterization of high performance electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Hong, Jian

    Lithium-ion batteries have revolutionized portable electronics. Electrode reactions in these electrochemical systems are based on reversible intercalation of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive and higher capacity electrode materials will be required. The olivine phase lithium iron phosphate has attracted the most attention because of its low cost and safety (high thermal and chemical stability). However, it is an intriguing fundamental problem to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO 4 system. This thesis focuses on determining the rate-limit step of LiFePO4. First, a LiFePO4 material, with vanadium substituting on the P-site, was synthesized, and found that the crystal structure change may cause high lithium diffusivity. Since an accurate Li diffusion coefficient cannot be measured by traditional electrochemical method in a three-electrode cell due to the phase transformation during measurement, a new method to measure the intrinsic electronic and ionic conductivity of mixed conductive LiFePO 4 was developed. This was based on the conductivity measurements of mixed conductive solid electrolyte using electrochemical impedance spectroscopy (EIS) and blocking electrode. The effects of ionic/electronic conductivity and phase transformation on the rate performance of LiFePO4 were also first investigated by EIS and other electrochemical technologies. Based on the above fundamental kinetics studies, an optimized LiFePO4 was used as a target to deposit 1mum LiFePO4 thin film at Oak Ridge National Laboratory using radio frequency (RF) magnetron sputtering. Similar to the carbon coated LiFePO4 powder electrode, the carbon-contained RF LiFePO4 film with no preferential orientation showed excellent capacity and rate capability both at 25°C and -20

  15. Biomimetic nanostructuring of copper thin films enhances adhesion to the negative electrode laminate in lithium-ion batteries.

    PubMed

    Zheng, Ziyan; Wang, Zhihui; Song, Xiangyun; Xun, Shidi; Battaglia, Vincent; Liu, Gao

    2014-10-01

    Thin films of copper are widely used as current collectors for the negative electrodes in lithium-ion batteries. However, a major cause of battery failure is delamination between the current collector and the graphite anode. When silicon or tin is used as active material, delamination becomes a key issue owing to the large volume changes of these materials during lithation and delithation processes. Learning from Nature, we developed a new biomimetic approach based on the adhesion properties of the feet of geckos. The biomimetic approach improves adhesion between the laminate and the copper surface by introducing an array of Cu(OH)2 nanorods, which increases the surface area of the current collector. When graphite anode laminate is casted onto regular and a modified copper surfaces, the modified current collector displays superior adhesion to graphite and the PVDF binder-based electrode. The electrochemical performance of the batteries using these electrodes is not compromised by the additional chemistry of the Cu(OH)2 on the copper surface. The technique can lead to enhanced battery lifetimes over long-term cycling. PMID:25139044

  16. Sandwich electrode designed for high performance lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Zhao, Chunsong; Luo, Xi; Chen, Chengmeng; Wu, Hui

    2016-05-01

    We fabricated a sandwich structure Li-ion battery electrode by trapping micron-sized silicon between a copper current collector and a graphene coating. During dynamic electrochemical cycles, the volume change of the silicon can be buffered by the coating through the deformation of soft graphenes. This structure can effectively prevent the silicon particles from escaping from the current collector while keeping the buffered graphene coating integrated and unbroken during deformation. The electrodes could be maintained for 400 cycles at a constant charge capacity of 1000 mA h g-1.We fabricated a sandwich structure Li-ion battery electrode by trapping micron-sized silicon between a copper current collector and a graphene coating. During dynamic electrochemical cycles, the volume change of the silicon can be buffered by the coating through the deformation of soft graphenes. This structure can effectively prevent the silicon particles from escaping from the current collector while keeping the buffered graphene coating integrated and unbroken during deformation. The electrodes could be maintained for 400 cycles at a constant charge capacity of 1000 mA h g-1. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09049k

  17. Studies on two classes of positive electrode materials for lithium-ion batteries

    SciTech Connect

    Wilcox, James Douglas

    2008-12-01

    The development of advanced lithium-ion batteries is key to the success of many technologies, and in particular, hybrid electric vehicles. In addition to finding materials with higher energy and power densities, improvements in other factors such as cost, toxicity, lifetime, and safety are also required. Lithium transition metal oxide and LiFePO4/C composite materials offer several distinct advantages in achieving many of these goals and are the focus of this report. Two series of layered lithium transition metal oxides, namely LiNi1/3Co1/3-yMyMn1/3O2 (M=Al, Co, Fe, Ti) and LiNi0.4Co0.2-yMyMn0.4O2 (M = Al, Co, Fe), have been synthesized. The effect of substitution on the crystal structure is related to shifts in transport properties and ultimately to the electrochemical performance. Partial aluminum substitution creates a high-rate positive electrode material capable of delivering twice the discharge capacity of unsubstituted materials. Iron substituted materials suffer from limited electrochemical performance and poor cycling stability due to the degradation of the layered structure. Titanium substitution creates a very high rate positive electrode material due to a decrease in the anti-site defect concentration. LiFePO4 is a very promising electrode material but suffers from poor electronic and ionic conductivity. To overcome this, two new techniques have been developed to synthesize high performance LiFePO4/C composite materials. The use of graphitization catalysts in conjunction with pyromellitic acid leads to a highly graphitic carbon coating on the surface of LiFePO4 particles. Under the proper conditions, the room temperature electronic conductivity can be improved by nearly five orders of magnitude over untreated materials. Using Raman spectroscopy, the improvement in conductivity and rate performance of

  18. Lithium iron phosphate battery electrode integrity following high speed pulsed laser cutting

    NASA Astrophysics Data System (ADS)

    Lutey, Adrian H. A.; Fiorini, Maurizio; Fortunato, Alessandro; Carmignato, Simone

    2015-05-01

    Laser exposures are performed on lithium iron phosphate battery electrodes at with process parameters based on those leading to the smallest heat affected zone for low power laser exposure at . Scanning electron microscopy and Raman analysis are performed along the resulting cut edges to characterize macroscopic, chemical and microstructural changes resulting from laser exposure. The increase in velocity with respect to previous studies is found to limit macroscopic changes to areas directly exposed to the laser beam and greatly suppress or completely eliminate microstructural and chemical changes resulting from thermal conduction effects in the metallic conductor layers. These results confirm laser technology as a viable, more flexible solution to mechanical blanking devices for the cutting of lithium iron phosphate battery electrode films.

  19. Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries

    PubMed Central

    David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

    2016-01-01

    Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm−2) delivers a charge capacity of ∼588 mAh g−1electrode (∼393 mAh cm−3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries. PMID:27025781

  20. Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries.

    PubMed

    David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

    2016-01-01

    Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm(-2)) delivers a charge capacity of ∼588 mAh g(-1)electrode (∼393 mAh cm(-3)electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries. PMID:27025781

  1. Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

    2016-03-01

    Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm-2) delivers a charge capacity of ~588 mAh g-1electrode (~393 mAh cm-3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

  2. Graphene Oxide-Based Electrode Inks for 3D-Printed Lithium-Ion Batteries.

    PubMed

    Fu, Kun; Wang, Yibo; Yan, Chaoyi; Yao, Yonggang; Chen, Yanan; Dai, Jiaqi; Lacey, Steven; Wang, Yanbin; Wan, Jiayu; Li, Tian; Wang, Zhengyang; Xu, Yue; Hu, Liangbing

    2016-04-01

    All-component 3D-printed lithium-ion batteries are fabricated by printing graphene-oxide-based composite inks and solid-state gel polymer electrolyte. An entirely 3D-printed full cell features a high electrode mass loading of 18 mg cm(-2) , which is normalized to the overall area of the battery. This all-component printing can be extended to the fabrication of multidimensional/multiscale complex-structures of more energy-storage devices. PMID:26833897

  3. Use of amorphous tin-oxide films obtained by spray pyrolysis as electrodes in lithium batteries

    NASA Astrophysics Data System (ADS)

    Ayouchi, R.; Martin, F.; Ramos Barrado, J. R.; Martos, M.; Morales, J.; Sánchez, L.

    Amorphous tin-oxide films were prepared by spray pyrolysis of SnCl 2·2H 2O mixed with CH 3-COOH and deposited onto a stainless steel substrate at mild temperatures (350°C). The films grown were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). Also, they were tested as electrodes in lithium rechargeable batteries. The XPS results suggest that the substrate is thoroughly coated and that the films are composed mainly of SnO and SnO 2. These films exhibit good charge-discharge properties over more than 100 cycles. Heating at 600°C causes significant changes in their surface composition, in the virtual disappearance of the tin component and in the presence of oxygen-bound Fe. Under these conditions, the reversible capacity dramatically fades and the cell behaves similarly to that made from uncoated substrate.

  4. Carbon-Rich Active Materials with Macrocyclic Nanochannels for High-Capacity Negative Electrodes in All-Solid-State Lithium Rechargeable Batteries.

    PubMed

    Sato, Sota; Unemoto, Atsushi; Ikeda, Takuji; Orimo, Shin-Ichi; Isobe, Hiroyuki

    2016-07-01

    A high-capacity electrode active material with macrocyclic nanochannels is developed for a negative electrode of lithium batteries. With appropriate design of the molecular and crystal structures, a ubiquitous chemical commonly available in reagent stocks of any chemistry laboratories, naphthalene, was transformed into a high-performance electrode material for all-solid-state lithium batteries. PMID:27173002

  5. Two- and three-electrode impedance spectroscopy of lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Song, J. Y.; Lee, H. H.; Wang, Y. Y.; Wan, C. C.

    The interfacial impedance between PVDF/HFP-based electrolytes and lithium metal continues to increase and attains a delicate kinetic equilibrium upon prolonged storage. The graphite anode, on the other hand, is found to remain inert towards the electrolytes. Its interfacial impedance does not vary with increasing storage time or in the presence of different lithium salts. In addition, it is found that the impedance of a Li-C half-cell consists of the impedances of two interfaces and is therefore often mistakenly used in the interpretation of the behaviour of a single carbon electrode. Thus, a three-electrode impedance study is required. It is found that an inductive loop appears in the low-frequency region of the impedance spectrum of a carbon electrode immediately after the first lithium-intercalation step, which probably implies that an adsorption-desorption phenomenon might exist at the interface. Moreover, another inductive effect, which arises from the connecting leads, also appears in the high-frequency region. Finally, the cathode is found to be the major source of cell impedance and increases with increasing cycle number.

  6. Electrode-supported thin α-alumina separators for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mi, Wanliang; Sharma, Gaurav; Dong, Xueliang; Jin, Yi; Lin, Y. S.

    2016-02-01

    Lithium ion batteries with an inorganic separator offer improved safety and enhanced reliability. The free-standing inorganic separators recently studied for lithium ion batteries are brittle and expensive. To address these issues, this paper reports the synthesis of a new and stable electrode-supported separator using a low-cost ceramic powder. Thin and porous α-Al2O3 separator films of thicknesses down to 40 μm were coated on Li4Ti5O12 (LTO) electrode by blade-coating a slurry of α-Al2O3, water and a small amount of polyvinyl alcohol (PVA). The performance of the LTO/Li cells with coated α-Al2O3 separator improves with decreasing PVA content. Cells with coated α-Al2O3 separator containing 0.4wt% PVA exhibit similar discharge capacity but better rate capability than those with commercial polypropylene (PP) or thick sintered α-Al2O3 separator. The coated α-Al2O3 separator does not react with LTO even after many charge/discharge cycles. Fabrication of the electrode-supported α-Al2O3 separator is scalable and cost-effective, offering high potential for practical application in industrial lithium ion battery manufacturing.

  7. Silicon Nanowire Fabric as a Lithium Ion Battery Electrode Material

    SciTech Connect

    Chockla, Aaron M.; Harris, Justin T.; Akhavan, Vahid A.; Bogart, Timothy D.; Holmberg, Vincent C.; Steinhagen, Chet; Mullins, C. Buddie; Stevenson, Keith J.; Korgel, Brian A.

    2011-11-09

    A nonwoven fabric with paperlike qualities composed of silicon nanowires is reported. The nanowires, made by the supercritical-fluid–liquid–solid process, are crystalline, range in diameter from 10 to 50 nm with an average length of >100 μm, and are coated with a thin chemisorbed polyphenylsilane shell. About 90% of the nanowire fabric volume is void space. Thermal annealing of the nanowire fabric in a reducing environment converts the polyphenylsilane coating to a carbonaceous layer that significantly increases the electrical conductivity of the material. This makes the nanowire fabric useful as a self-supporting, mechanically flexible, high-energy-storage anode material in a lithium ion battery. Anode capacities of more than 800 mA h g{sup –1} were achieved without the addition of conductive carbon or binder.

  8. Deuterium and lithium-6 MAS NMR studies of manganese oxide electrode materials

    NASA Astrophysics Data System (ADS)

    Paik, Younkee

    Electrolytic manganese dioxide (EMD) is used world wide as the cathode materials in both lithium and alkaline primary (non-rechargeable) batteries. We have developed deuterium and lithium MAS NMR techniques to study EMD and related manganese oxides and hydroxides, where diffraction techniques are of limited value due to a highly defective nature of the structures. Deuterons in EMD, manganite, groutite, and deuterium-intercalated pyrolusite and ramsdellite were detected by NMR, for the first time, and their locations and motions in the structures were analyzed by applying variable temperature NMR techniques. Discharge mechanisms of EMD in alkaline (aqueous) electrolytes were studied, in conjunction with step potential electrochemical spectroscopic (SPECS) method, and five distinctive discharge processes were proposed. EMD is usually heat-treated at about 300--400°C to remove water to be used in lithium batteries. Details of the effects of heat-treatment, such as structural and compositional changes as a function of heat-treatment temperature, were studied by a combination of MAS NMR, XRD, and thermogravimetric analysis. Lithium local environments in heat-treated EMD (HEMD) that were discharged in lithium cells, were described in terms of related environments found in model compounds pyrolusite and ramsdellite where specific Li + sites were detected by MAS NMR and the hyperfine shift scale method of Grey et al. Acid-leaching of Li2MnO3 represents an approach for synthesizing new or modified manganese oxide electrode materials for lithium rechargeable batteries. Progressive removal of lithium from specific crystallographic sites, followed by a gradual change of the crystal structure, was monitored by a combination of NMR and XRD techniques.

  9. Effect of electrode compression on the wettability of lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Sang Gun; Jeon, Dong Hyup

    2014-11-01

    Using the multiphase lattice Boltzmann method (LBM), the electrolyte transport dynamics in the two-dimensional electrode structure of a lithium-ion battery are simulated. The effect of the compression ratio of a porous electrode on wettability is explored with respect to variations of porosity and particle shape. The electrolyte distribution in the electrode and the electrolyte saturation profile are examined in order to evaluate the wetting capability at various compression ratios. The results show that wettability in the electrode decreases as the compression ratio increases. In a highly compressed electrode, the through-plane permeation of liquid electrolyte is small. Thus, the electrolytes are mainly observed at the interface of the electrode and separator. The anode has lower wettability than the cathode due to the deformation of particle shape during the manufacturing process. Therefore, particle shape has a strong effect on wettability. The two-dimensional LBM approach used in this study characterizes the electrolyte transport phenomena inside the electrode and allows us to compare the wettability between the cathode and anode at various compression ratios.

  10. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

    Singh, Prabhakar; Ruka, Roswell J.

    1992-01-01

    An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

  11. Analysis of the Galvanostatic Intermittent Titration Technique (GITT) as applied to a lithium-Ion porous electrode.

    SciTech Connect

    Dees, D. W.; Kawauchi, S.; Abraham, D. P.; Prakash, J.; Chemical Sciences and Engineering Division; Toyota Central R&D Labs Inc.; Illinois Inst. of Tech.

    2009-04-01

    Galvanostatic Intermittent Titration Technique (GITT) experiments were conducted to determine the lithium diffusion coefficient of LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}, used as the active material in a lithium-ion battery porous composite positive electrode. An electrochemical model, based on concentrated solution porous electrode theory, was developed to analyze the GITT experimental results and compare to the original GITT analytical theory. The GITT experimental studies on the oxide active material were conducted between 3.5 and 4.5 V vs. lithium, with the maximum lithium diffusion coefficient value being 10{sup -10} cm{sup 2} s{sup -1} at 3.85 V. The lithium diffusion coefficient values obtained from this study agree favorably with the values obtained from an earlier electrochemical impedance spectroscopy study.

  12. Experimental investigation of a thermionic converter with developed surface electrodes

    SciTech Connect

    Luke, J.R.; El-Genk, M.S.; Adrian, J.M.

    1997-01-01

    A thermionic converter with developed planar electrode surfaces is designed and tested. One of the electrodes has concentric circular grooves cut into its surface, while the other electrode surface is smooth. The grooves are 0.5 mm deep and 0.5 mm wide, having lands that are 1.0 mm wide. The experimental setup is flexible so that either the smooth or developed surface electrode can be operated as the emitter, with the other operating as the collector. The I-V characteristics and power output are compared for the two electrode arrangements. {copyright} {ital 1997 American Institute of Physics.}

  13. Three dimensional studies of particle failure in silicon based composite electrodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Gonzalez, Joseph; Sun, Ke; Huang, Meng; Lambros, John; Dillon, Shen; Chasiotis, Ioannis

    2014-12-01

    Silicon based composite electrodes for lithium ion batteries are of significant interest because of their potential to be high capacity alternatives to the commonly used graphitic carbon anodes. A drawback to their use, however, is the Si particle debonding and fracture that occurs as a result of the volumetric expansion by the lithium host particles upon lithiation of the anode electrode. We use X-ray micro computed tomography to visualize the evolution of the internal microstructure of a silicon-based electrode before and after four lithiation steps during the first half cycle of the cell. We develop a novel threshold edge detect method to perform 3D volumetric measurements of silicon particle expansion. According to our results, 100% lithiation of the composite anode resulted in up to 290% volume expansion of individual Si particles. Furthermore, the global and localized image intensity histogram profiles from 3D data were used to analyze the silicon particle X-ray attenuation effects as a function of lithiation: a decreasing attenuation with lithiation and the propagation of the reaction front through a core-shell process between the original state and 25% lithiation of the silicon-based electrode have been observed.

  14. Biomass-derived carbonaceous positive electrodes for sustainable lithium-ion storage

    NASA Astrophysics Data System (ADS)

    Liu, Tianyuan; Kavian, Reza; Chen, Zhongming; Cruz, Samuel S.; Noda, Suguru; Lee, Seung Woo

    2016-02-01

    Biomass derived carbon materials have been widely used as electrode materials; however, in most cases, only electrical double layer capacitance (EDLC) is utilized and therefore, only low energy density can be achieved. Herein, we report on redox-active carbon spheres that can be simply synthesized from earth-abundant glucose via a hydrothermal process. These carbon spheres exhibit a specific capacity of ~210 mA h gCS-1, with high redox potentials in the voltage range of 2.2-3.7 V vs. Li, when used as positive electrode in lithium cells. Free-standing, flexible composite films consisting of the carbon spheres and few-walled carbon nanotubes deliver high specific capacities up to ~155 mA h gelectrode-1 with no obvious capacity fading up to 10 000 cycles, proposing to be promising positive electrodes for lithium-ion batteries or capacitors. Furthermore, considering that the carbon spheres were obtained in an aqueous glucose solution and no toxic or hazardous reagents were used, this process opens up a green and sustainable method for designing high performance, environmentally-friendly energy storage devices.Biomass derived carbon materials have been widely used as electrode materials; however, in most cases, only electrical double layer capacitance (EDLC) is utilized and therefore, only low energy density can be achieved. Herein, we report on redox-active carbon spheres that can be simply synthesized from earth-abundant glucose via a hydrothermal process. These carbon spheres exhibit a specific capacity of ~210 mA h gCS-1, with high redox potentials in the voltage range of 2.2-3.7 V vs. Li, when used as positive electrode in lithium cells. Free-standing, flexible composite films consisting of the carbon spheres and few-walled carbon nanotubes deliver high specific capacities up to ~155 mA h gelectrode-1 with no obvious capacity fading up to 10 000 cycles, proposing to be promising positive electrodes for lithium-ion batteries or capacitors. Furthermore, considering

  15. Binder-free nitrogen-doped carbon nanotubes electrodes for lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Lin, Xiujing; Lu, Xu; Huang, Tao; Liu, Zhaolin; Yu, Aishui

    2013-11-01

    Here the binder-free nickel foam supported nitrogen-doped carbon nanotubes (N-CNTs@Ni) are synthesized by a floating catalyst chemical vapor deposition (FCCVD) method. Without any additional treatment, it could be employed as the air electrode in the lithium-oxygen batteries and delivers 1814 mAh g-1 (normalized to the weight of the air electrode) at the current density of 0.05 mA cm-2. The loose packing 3-dimension network structure facilitates the O2 diffusion in the inner electrode and provides enough void volume for the products deposition during discharge process. The improved contact between N-CNTs and the current collector Ni is beneficial to suppress the volume expansion and leads to less polarization as well as good cycling performance.

  16. A 3.6V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Recham, N.; Chotard, J.-N.; Dupont, L.; Delacourt, C.; Walker, W.; Armand, M.; Tarascon, J.-M.

    2010-01-01

    Li-ion batteries have contributed to the commercial success of portable electronics, and are now in a position to influence higher-volume applications such as plug-in hybrid electric vehicles. Most commercial Li-ion batteries use positive electrodes based on lithium cobalt oxides. Despite showing a lower voltage than cobalt-based systems (3.45V versus 4V) and a lower energy density, LiFePO4 has emerged as a promising contender owing to the cost sensitivity of higher-volume markets. LiFePO4 also shows intrinsically low ionic and electronic transport, necessitating nanosizing and/or carbon coating. Clearly, there is a need for inexpensive materials with higher energy densities. Although this could in principle be achieved by introducing fluorine and by replacing phosphate groups with more electron-withdrawing sulphate groups, this avenue has remained unexplored. Herein, we synthesize and show promising electrode performance for LiFeSO4F. This material shows a slightly higher voltage (3.6V versus Li) than LiFePO4 and suppresses the need for nanosizing or carbon coating while sharing the same cost advantage. This work not only provides a positive-electrode contender to rival LiFePO4, but also suggests that broad classes of fluoro-oxyanion materials could be discovered.

  17. A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries.

    PubMed

    Recham, N; Chotard, J-N; Dupont, L; Delacourt, C; Walker, W; Armand, M; Tarascon, J-M

    2010-01-01

    Li-ion batteries have contributed to the commercial success of portable electronics, and are now in a position to influence higher-volume applications such as plug-in hybrid electric vehicles. Most commercial Li-ion batteries use positive electrodes based on lithium cobalt oxides. Despite showing a lower voltage than cobalt-based systems (3.45 V versus 4 V) and a lower energy density, LiFePO(4) has emerged as a promising contender owing to the cost sensitivity of higher-volume markets. LiFePO(4) also shows intrinsically low ionic and electronic transport, necessitating nanosizing and/or carbon coating. Clearly, there is a need for inexpensive materials with higher energy densities. Although this could in principle be achieved by introducing fluorine and by replacing phosphate groups with more electron-withdrawing sulphate groups, this avenue has remained unexplored. Herein, we synthesize and show promising electrode performance for LiFeSO(4)F. This material shows a slightly higher voltage (3.6 V versus Li) than LiFePO(4) and suppresses the need for nanosizing or carbon coating while sharing the same cost advantage. This work not only provides a positive-electrode contender to rival LiFePO(4), but also suggests that broad classes of fluoro-oxyanion materials could be discovered. PMID:19946280

  18. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Johnson, Rolland P.; Han, B.; Murray, S. N.; Pennisi, T. R.; Santana, M.; Stockli, Martin P.; Welton, R. F.

    2011-09-26

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H{sup -} ion generation was increased by up to a factor of 5 by plasma electrode 'activation', without supplying additional Cs, by heating the collar to high temperature for several hours using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, optimum cesiation was produced (without additional Cs) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces. Such activation by accumulation of impurities on electrode surfaces can be a reason for H{sup -} emission enhancement in other so-called 'volume' negative ion sources.

  19. Improved Positive Electrode Materials for Lithium-ion Batteries

    NASA Astrophysics Data System (ADS)

    Conry, Thomas Edward

    The introduction of the first commercially produced Li-ion battery by Sony in 1990 sparked a period of unprecedented growth in the consumer electronics industry. Now, with increasing efforts to move away from fossil-fuel-derived energy sources, a substantial amount of current research is focused on the development of an electrified transportation fleet. Unfortunately, existent battery technologies are unable to provide the necessary performance for electric vehicles (EV's) and plug-in hybrid electric vehicles (PHEV's) vehicles at a competitive cost. The cost and performance metrics of current Li-ion batteries are mainly determined by the positive electrode materials. The work here is concerned with understanding the structural and electrochemical consequences of cost-lowering mechanisms in two separate classes of Li-ion cathode materials; the LiMO2 (M = Ni, Mn, Co) layered oxides and the LiMPO4 olivine materials; with the goal of improving performance. Al-substitution for Co in LiNizMnzCo1-2zO 2 ("NMC") materials not only decreases the costly Co-content, but also improves the safety aspects and, notably, enhances the cycling stability of the layered oxide electrodes. The structural and electrochemical effects of Al-substitution are investigated here in a model NMC compound, LiNi0.45 Mn0.45Co0.1-yAlyO2. In addition to electrochemical measurements, various synchrotron-based characterization methods are utilized, including high-resolution X-ray diffraction (XRD), in situ X-ray diffraction, and X-ray absorption spectroscopy (XAS). Al-substitution causes a slight distortion of the as-synthesized hexagonal layered oxide lattice, lowering the inherent octahedral strain within the transition metal layer. The presence of Al also is observed to limit the structural variation of the NMC materials upon Li-deintercalation, as well as extended cycling of the electrodes. Various olivine materials, Li

  20. Vertical distribution of overpotentials and irreversible charge losses in lithium ion battery electrodes.

    PubMed

    Klink, Stefan; Schuhmann, Wolfgang; La Mantia, Fabio

    2014-08-01

    Porous lithium ion battery electrodes are characterized using a vertical distribution of cross-currents. In an appropriate simplification, this distribution can be described by a transmission line model (TLM) consisting of infinitely thin electrode layers. To investigate the vertical distribution of currents, overpotentials, and irreversible charge losses in a porous graphite electrode in situ, a multi-layered working electrode (MWE) was developed as the experimental analogue of a TLM. In this MWE, each layer is in ionic contact but electrically insulated from the other layers by a porous separator. It was found that the negative graphite electrodes get lithiated and delithiated stage-by-stage and layer-by-layer. Several mass-transport- as well as non-mass-transport-limited processes could be identified. Local current densities can reach double the average, especially on the outermost layer at the beginning of each intercalation stage. Furthermore, graphite particles close to the counter electrode act as "electrochemical sieve" reducing the impurities present in the electrolyte such as water. PMID:24989450

  1. Evaporated Lithium Surface Coatings in NSTX

    SciTech Connect

    Kugel, H. W.; Mansfield, D.; Maingi, R.; Bel, M. G.; Bell, R. E.; Allain, J. P.; Gates, D.; Gerhardt, S.; Kaita, R.; Kallman, J.; Kaye, S.; LeBlanc, B.; Majeski, R.; Menard, J.; Mueller, D.; Ono, M.

    2009-04-09

    Two lithium evaporators were used to evaporate more than 100 g of lithium on to the NSTX lower divertor region. Prior to each discharge, the evaporators were withdrawn behind shutters, where they also remained during the subsequent HeGDC applied for periods up to 9.5 min. After the HeGDC, the shutters were opened and the LITERs were reinserted to deposit lithium on the lower divertor target for 10 min, at rates of 10-70 mg/min, prior to the next discharge. The major improvements in plasma performance from these lithium depositions include: 1) plasma density reduction as a result of lithium deposition; 2) suppression of ELMs; 3) improvement of energy confinement in a low-triangularity shape; 4) improvement in plasma performance for standard, high-triangularity discharges; 5) reduction of the required HeGDC time between discharges; 6) increased pedestal electron and ion temperature; 7) reduced SOL plasma density; and 8) reduced edge neutral density.

  2. 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. PMID:27028048

  3. Biomass-derived carbonaceous positive electrodes for sustainable lithium-ion storage.

    PubMed

    Liu, Tianyuan; Kavian, Reza; Chen, Zhongming; Cruz, Samuel S; Noda, Suguru; Lee, Seung Woo

    2016-02-14

    Biomass derived carbon materials have been widely used as electrode materials; however, in most cases, only electrical double layer capacitance (EDLC) is utilized and therefore, only low energy density can be achieved. Herein, we report on redox-active carbon spheres that can be simply synthesized from earth-abundant glucose via a hydrothermal process. These carbon spheres exhibit a specific capacity of ∼210 mA h gCS(-1), with high redox potentials in the voltage range of 2.2-3.7 V vs. Li, when used as positive electrode in lithium cells. Free-standing, flexible composite films consisting of the carbon spheres and few-walled carbon nanotubes deliver high specific capacities up to ∼155 mA h gelectrode(-1) with no obvious capacity fading up to 10,000 cycles, proposing to be promising positive electrodes for lithium-ion batteries or capacitors. Furthermore, considering that the carbon spheres were obtained in an aqueous glucose solution and no toxic or hazardous reagents were used, this process opens up a green and sustainable method for designing high performance, environmentally-friendly energy storage devices. PMID:26809548

  4. Investigation of the Gas-Diffusion-Electrode Used as Lithium/Air Cathode in Non-aqueous Electrolyte and the Importance of Carbon Material Porosity

    SciTech Connect

    Qu, D.; Yang, X.; Tran, C.

    2010-04-02

    The gas-diffusion-electrode used in a Li-air cell has been studied in a unique homemade electrochemical cell. Three major obstacles for the development of a feasible Li-air system were discussed with a focus on the development of a functional gas-diffusion-electrode in non-aqueous electrolytes and the way of avoiding the passivation of gas-diffusion-electrodes caused by the deposition of the reduction products. It is the first time that the importance of establishing the 3-phase electrochemical interface in non-aqueous electrolyte is demonstrated by creating air-diffusion paths and an air saturated portion for an air cathode. A model mechanism of electrode passivation by the reaction products was also proposed. Lithium oxides formed during O{sub 2} reduction tend to block small pores, preventing them from further utilization in the electrochemical reaction. On the other hand, lithium oxides would accumulate inside the large pores during the reduction until the density of oxides becomes high enough to choke-off the mass transfer. Carbon materials with a high surface area associated with larger pores should be selected to make the gas-diffusion-electrode for Li-air battery. For the first time, a near linear relationship between the capacity of GDE in a non-aqueous electrolyte and the average pore diameter was demonstrated, which could be used to estimate the capacity of the GDE quantitatively.

  5. Stripe- or square-patterned arrays of tin dioxide nanowires for use in lithium-ion battery electrodes

    NASA Astrophysics Data System (ADS)

    Lee, Sang Ho; Kim, Won Bae

    2016-03-01

    This paper reports a novel electrode design for use in electrochemical lithium-ion storage. 3-dimensional patterns of tin dioxide nanowires that are grown directly over current collectors are suggested as electrode frameworks, representing the synergetic combination of nanometer-sized 1-dimensional electrode materials and micrometer-scaled hollow channels formed between the patterned nanowire arrays. The lithium-ion storage properties are investigated by changing the pattern geometries of these nanowire arrays in the shape of stripes and squares. The proposed electrode platforms show the enhanced electrochemical storage performances, which might be attributed to the effective diffusion of liquid phase electrolyte through the hollow channels between these patterned nanowire arrays. More interestingly, with increasing the hollow channels in these proposed systems, the high-rate performance and cycling stability are improved even further due to the structural effect of these electrode frameworks.

  6. Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

    DOE PAGESBeta

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; Kim, Gi -Heon; Mukherjee, Partha P.

    2015-06-17

    In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constantmore » voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.« less

  7. Reduced order modeling of mechanical degradation induced performance decay in lithium-ion battery porous electrodes

    SciTech Connect

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; Kim, Gi -Heon; Mukherjee, Partha P.

    2015-06-17

    In this paper, a one-dimensional computational framework is developed that can solve for the evolution of voltage and current in a lithium-ion battery electrode under different operating conditions. A reduced order model is specifically constructed to predict the growth of mechanical degradation within the active particles of the carbon anode as a function of particle size and C-rate. Using an effective diffusivity relation, the impact of microcracks on the diffusivity of the active particles has been captured. Reduction in capacity due to formation of microcracks within the negative electrode under different operating conditions (constant current discharge and constant current constant voltage charge) has been investigated. At the beginning of constant current discharge, mechanical damage to electrode particles predominantly occurs near the separator. As the reaction front shifts, mechanical damage spreads across the thickness of the negative electrode and becomes relatively uniform under multiple discharge/charge cycles. Mechanical degradation under different drive cycle conditions has been explored. It is observed that electrodes with larger particle sizes are prone to capacity fade due to microcrack formation. Finally, under drive cycle conditions, small particles close to the separator and large particles close to the current collector can help in reducing the capacity fade due to mechanical degradation.

  8. State of health estimation in composite electrode lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Bartlett, Alexander; Marcicki, James; Rhodes, Kevin; Rizzoni, Giorgio

    2015-06-01

    Electrochemical models of lithium-ion batteries have been increasingly considered for online state of health estimation. These models can more accurately predict cell performance than traditional circuit models and can better relate physical degradation mechanisms to changes in model parameters. However, examples of state of health estimation algorithms that are validated with experimental data are scarce in the literature, particularly for cells with a composite electrode. The individual electrode active materials in a composite electrode may degrade at different rates and according to different physical mechanisms, and online estimation of this degradation facilitates more robust knowledge of how battery performance changes over its life. In this paper we use a reduced-order electrochemical model for a composite LiMn2O4-LiNi1/3Mn1/3 Co1/3O2 (LMO-NMC) electrode cell for online estimation of active material loss. Experimental data collected from composite electrode half cells that were aged under constant current cycling are used in an extended Kalman filter to estimate model parameters associated with loss of each active material. The capacity loss predicted by the online estimates agrees well with the measured capacity loss. Additionally, a differential capacity analysis demonstrates that active materials lose capacity at a similar rate, the same conclusion obtained from the online estimation algorithm.

  9. Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

    NASA Astrophysics Data System (ADS)

    Travis, Jonathan

    The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films

  10. Low-temperature study of lithium-ion cells using a Li ySn micro-reference electrode

    NASA Astrophysics Data System (ADS)

    Jansen, Andrew N.; Dees, Dennis W.; Abraham, Daniel P.; Amine, Khalil; Henriksen, Gary L.

    Lithium-ion batteries are considered to be the next battery system for hybrid electric vehicles (HEVs) due to their high power density. However, their power is severely limited at -30 °C and the concern exists that lithium metal could plate on the negative electrode during regen (charge) pulses. The goal of this work is to determine the reason for this poor low-temperature performance using an in situ Li ySn micro reference electrode (RE) over a wide temperature range of 30 °C to -30 °C. A variety of negative and positive electrode materials with unique morphologies was used in this work to help elucidate the dominant low-temperature mechanism. In this work, it was observed that the potential of graphite negative electrodes does dip below lithium potentials not only during charge pulses, but also under normal charging if the cell cutoff voltage is not reduced from its room-temperature setting of 4.1 V, whereas hard carbon electrodes do not because they operate further from lithium potential. The most surprising finding from this work was that a second impedance mechanism dominates below 0 °C that affects the positive and negative electrodes almost equally. This suggests that the responsible phenomenon is independent of the active material and is most likely a pure electrolyte-interface effect.

  11. Designing an elastomeric binder for large-volume-change electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Zonghai

    It is of commercial importance to develop high capacity negative and positive electrode materials for lithium-ion batteries to meet the energy requirements of portable electronic devices. Excellent capacity retention has been achieved for thin sputtered films of amorphous Si, Ge and Si-Sn alloys even when cycled to 2000 mAh/g and above, which suggests that amorphous alloys are capable of extended cycling. However, PVDF-based composite electrodes incorporating a-Si0.64Sn0.36/Ag powder (10 wt% silver coating) (˜10mum) still suffer from severe capacity fading because of the huge volumetric changes of a-Si0.64Sn0.36/Ag during charge/discharge cycling. It is the objective of this thesis to understand the problem scientifically and to propose practical solutions to solve this problem. Mechanical studies of binders for lithium battery electrodes have never been reported in the literature. The mechanical properties of commonly used binders, such as poly(vinylidene fluoride) (PVDF), haven't been challenged because commercially used active materials, such as LiCoO2 and graphite, have small volumetric changes (<10%) during charge/discharge cycling. However, the recently proposed metallic alloys have huge volumetric changes (up to 250%) during cycling. In this case, the mechanical properties of the binder become critical. A tether model is proposed to qualitatively understand the capacity fading of high-volume-change electrodes, and to predict the properties of a good binder system. A crosslinking/coupling route was used to modify the binder system according to the requirements of the tether model. A poly(vinylidene fluoride-tetrafluoroethylenepropylene)-based elastomeric binder system was designed to successfully improve the capacity retention of a-Si0.64 Sn0.36/Ag composite electrodes. In this thesis, it has also proven nontrivial to maximize the capacity retention of large-volume-change electrodes even when a fixed elastomeric binder system was used. The parameters that

  12. Electrolyte incorporation into composite electrodes for proton-exchange membrane fuel cells and lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Oh, Jung Min

    2011-12-01

    This dissertation describes research on the preparation and characterization of composite electrodes for use in proton-exchange membrane (PEM) fuel cells and lithium ion batteries. The general focus of the research was on high-surface-area carbon supports for platinum catalysts in fuel cells, and integration of electrolytes, particularly fluoropolymer electrolytes, into composite electrodes both batteries and fuel cells. Results are described for work in the following three specific topical areas. (1) Carbon nanofibers for use as platinum (Pt) catalyst supports in fuel cells were prepared by carbonization of electrospun acrylic fibers. The resulting carbon nanofibers were found to contain mainly micropores. Following grinding to a powder form, the carbon nanofibers were used as supports for Pt nanoparticles. The pulverized carbon nanofibers were found to be not suitable as supports for Pt catalysts because the microporosity of the individual carbon nanofibers cannot provide continuous porous channels in the electrode. As a result, the Pt utilization was found to be low. (2) Mesoporous carbon composites containing nanoscale embedded zirconia particles (ZCS) were prepared and found to be highly porous and electrically conductive. Surface modification of the composites with organic compounds having phenylphosphonic acid groups (e.g., phenylphosphonic acid, m-sulfophenylphosphonic acid, or sulfonated fluoropolymer ionomer having terminal phosphonic acid groups) was accomplished by simple exposure of the carbon composite to organophosphonate solutions. Nanoscale ZrO2 surfaces present in the composite skeleton acted as reactive sites for anchoring of phosphonates through formation of robust Zr--O--P bonding. Proton-exchange sites were introduced onto the nanocomposite surface by grafting m-sulfophenylphosphonic acid or a sulfonated fluoropolymer ionomer. Modification with the ionomer provided an increase in proton-exchange capacity relative to that found following

  13. A Free-Standing Sulfur/Nitrogen-Doped Carbon Nanotube Electrode for High-Performance Lithium/Sulfur Batteries.

    PubMed

    Zhao, Yan; Yin, Fuxing; Zhang, Yongguang; Zhang, Chengwei; Mentbayeva, Almagul; Umirov, Nurzhan; Xie, Hongxian; Bakenov, Zhumabay

    2015-12-01

    A free-standing sulfur/nitrogen-doped carbon nanotube (S/N-CNT) composite prepared via a simple solution method was first studied as a cathode material for lithium/sulfur batteries. By taking advantage of the self-weaving behavior of N-CNT, binders and current collectors are rendered unnecessary in the cathode, thereby simplifying its manufacturing and increasing the sulfur weight ratio in the electrode. Transmission electronic microscopy showed the formation of a highly developed core-shell tubular structure consisting of S/N-CNT composite with uniform sulfur coating on the surface of N-CNT. As a core in the composite, the N-CNT with N functionalization provides a highly conductive and mechanically flexible framework, enhancing the electronic conductivity and consequently the rate capability of the material. PMID:26586150

  14. A Free-Standing Sulfur/Nitrogen-Doped Carbon Nanotube Electrode for High-Performance Lithium/Sulfur Batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Yan; Yin, Fuxing; Zhang, Yongguang; Zhang, Chengwei; Mentbayeva, Almagul; Umirov, Nurzhan; Xie, Hongxian; Bakenov, Zhumabay

    2015-11-01

    A free-standing sulfur/nitrogen-doped carbon nanotube (S/N-CNT) composite prepared via a simple solution method was first studied as a cathode material for lithium/sulfur batteries. By taking advantage of the self-weaving behavior of N-CNT, binders and current collectors are rendered unnecessary in the cathode, thereby simplifying its manufacturing and increasing the sulfur weight ratio in the electrode. Transmission electronic microscopy showed the formation of a highly developed core-shell tubular structure consisting of S/N-CNT composite with uniform sulfur coating on the surface of N-CNT. As a core in the composite, the N-CNT with N functionalization provides a highly conductive and mechanically flexible framework, enhancing the electronic conductivity and consequently the rate capability of the material.

  15. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Han, Baoxi; Johnson, Rolland P.; Murray Jr, S N; Pennisi, Terry R; Santana, Manuel; Stockli, Martin P; Welton, Robert F

    2011-01-01

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H- ion generation was increased by up to a factor of 5 by long time plasma electrode activation, without adding Cs from Cs supply, by heating the collar to high temperature using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, perfect cesiation was produced (without additional Cs supply) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces.

  16. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    NASA Technical Reports Server (NTRS)

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  17. Rock-salt-type lithium metal sulphides as novel positive-electrode materials

    PubMed Central

    Sakuda, Atsushi; Takeuchi, Tomonari; Okamura, Kazuhiro; Kobayashi, Hironori; Sakaebe, Hikari; Tatsumi, Kuniaki; Ogumi, Zempachi

    2014-01-01

    One way of increasing the energy density of lithium-ion batteries is to use electrode materials that exhibit high capacities owing to multielectron processes. Here, we report two novel materials, Li2TiS3 and Li3NbS4, which were mechanochemically synthesised at room temperature. When used as positive-electrode materials, Li2TiS3 and Li3NbS4 charged and discharged with high capacities of 425 mA h g−1 and 386 mA h g−1, respectively. These capacities correspond to those resulting from 2.5- and 3.5-electron processes. The average discharge voltage was approximately 2.2 V. It should be possible to prepare a number of high-capacity materials on the basis of the concept used to prepare Li2TiS3 and Li3NbS4. PMID:24811191

  18. TG-MS analysis of solid electrolyte interphase (SEI) on graphite negative-electrode in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Liwei; Watanabe, Izumi; Doi, Takayuki; Okada, Shigeto; Yamaki, Jun-ichi

    The thermal stability and chemical structure of solid electrolyte interphase (SEI) formed on a natural-graphite negative-electrode in ethylene carbonate (EC) and dimethyl carbonate (DMC)-based electrolyte was investigated by thermogravimetry-differential thermal analysis combined with mass spectrometry (TG-DTA/MS) and X-ray photoemission spectroscopy (XPS). Due to the decomposition of SEI, two CO 2 evolution peaks at around 330 and 430 °C were detected in TG-MS studies with continuous CO 2 background. The continuous CO 2 background was attributed to the gradual decomposition of oxygen-containing polymeric species of SEI. Another two dominant components of SEI, lithium alkyl carbonate and lithium oxalate, were found to contribute to the CO 2 peaks at 330 and 430 °C separately. The effects of charging-depth, current density and cycle number on the CO 2 distribution and XPS spectra were studied. It was found that lithium oxalate was reduction product of lithium alkyl carbonate during the intercalation of lithium ions. The reduction reaction could be accelerated by elevated temperature. The transformation of SEI chemical structure showed direct effect on the thermal stability of SEI. At the same time, lithium carbonate was also found in SEI on the graphite electrode after long cycles, while it was negligible in the electrode subjected to short cycles.

  19. Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

    PubMed

    Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

    2016-03-01

    Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery. PMID:26981849

  20. Effects of Carbonate Solvents and Lithium Salts on Morphology and Coulombic Efficiency of Lithium Electrode

    SciTech Connect

    Ding, Fei; Xu, Wu; Chen, Xilin; Zhang, Jian; Engelhard, Mark H.; Zhang, Yaohui; Johnson, Bradley R.; Crum, Jarrod V.; Blake, Thomas A.; Liu, Xingjiang; Zhang, Jiguang

    2013-09-04

    The application of lithium (Li) metal anode in rechargeable batteries is hindered by Li dendrite growth during Li deposition and low Li Coulombic efficiency (CE), where the nonaqueous electrolyte plays a critical role. In this work, the effects of different carbonate solvents and Li salts on Li deposition morphology and CE were systematically investigated. Typically cyclic carbonates are found to favor the formation of uniform Li film and improve Li CE than linear carbonates do. Several specific cyclic carbonates that are conventionally used as solid electrolyte interface formation additives in Li ion batteries can also improve the CE of Li anode. Furthermore, among the nine electrolyte salts studied, LiAsF6 and LiBOB lead to the highest CE for Li anode. LiBOB also leads to much smoother Li morphology than other salts do. Considering the better safety of LiBOB as compared to LiAsF6, LiBOB is a promising Li salt for rechargeable Li metal batteries with high CE. By combining the best electrolyte solvent/salt that can lead to high Li CE and novel electrolyte additives that can prevent dendrite formation, it is possible to find an electrolyte that not only prevents Li dendrite formation but also lead to high CE during Li deposition/stripping processes.

  1. Ultra-light Hierarchical Graphene Electrode for Binder-Free Supercapacitors and Lithium-Ion Battery Anodes.

    PubMed

    Zuo, Zicheng; Kim, Tae Young; Kholmanov, Iskandar; Li, Huifeng; Chou, Harry; Li, Yuliang

    2015-10-01

    A mild and environmental-friendly method is developed for fabricating a 3D interconnected graphene electrode with large-scale continuity. Such material has interlayer pores between reduced graphene oxide nanosheets and in-plane pores. Hence, a specific surface area up to 835 m(2) g(-1) and a high powder conductivity up to 400 S m(-1) are achieved. For electrochemical applications, the interlayer pores can serve as "ion-buffering reservoirs" while in-plane ones act as "channels" for shortening the mass cross-plane diffusion length, reducing the ion response time, and prevent the interlayer restacking. As binder-free supercapacitor electrode, it delivers a specific capacitance up to 169 F g(-1) with surface-normalized capacitance close to 21 μF cm(-2) (intrinsic capacitance) and power density up to 7.5 kW kg(-1), in 6 m KOH aqueous electrolyte. In the case of lithium-ion battery anode, it shows remarkable advantages in terms of the initiate reversible Coulombic efficiency (61.3%), high specific capacity (932 mAh g(-1) at 100 mA g(-1)), and robust long-term retention (93.5% after 600 cycles at 2000 mAh g(-1)). PMID:26153327

  2. Chemical and microstructural transformations in lithium iron phosphate battery electrodes following pulsed laser exposure

    NASA Astrophysics Data System (ADS)

    Lutey, Adrian H. A.; Fiorini, Maurizio; Fortunato, Alessandro; Ascari, Alessandro

    2014-12-01

    Multi-layer lithium iron phosphate (LFP) battery electrodes are exposed to nanosecond pulsed laser radiation of wavelength 1064 nm. Test parameters are chosen to achieve characteristic interaction types ranging from partial incision of the active coating layers only to complete penetration of the electrodes with high visual cut quality. Raman spectroscopy is performed on unexposed regions and at points approaching each incision, highlighting changes in chemical composition and microstructure in the heat affected zone (HAZ). Thermogravimetric analysis is performed on the unexposed electrode active materials to distinguish the development of compositional changes under conditions of slow heating below the melting and sublimation temperatures. A brief theoretical description of the physical phenomena taking place during laser exposure is provided in terms of direct ablation during each laser pulse and vaporization or thermal degradation due to conductive heat transfer on a much longer time-scale, with characteristics of the HAZ reported in terms of these changes. For all laser exposures carried out in the study, chemical and microstructural changes are limited to the visible HAZ. Some degree of oxidation and LFP olivine phase degradation is observed in the cathode, while the polycrystalline graphite structure becomes less ordered in the anode. Where complete penetration is achieved, melting of the cathode active layer and combustion of the anode active layer take place near the cut edge due to thermal conduction from the metallic conductive layers. The presented results provide insight into the effects of laser processing on LFP electrode integrity.

  3. On-chip lithium cells for electrical and structural characterization of single nanowire electrodes

    NASA Astrophysics Data System (ADS)

    Subramanian, A.; Hudak, N. S.; Huang, J. Y.; Zhan, Y.; Lou, J.; Sullivan, J. P.

    2014-07-01

    We present a transmission electron microscopy (TEM)-compatible, hybrid nanomachined, on-chip construct for probing the structural and electrical changes in individual nanowire electrodes during lithium insertion. We have assembled arrays of individual β-phase manganese dioxide (β-MnO2) nanowires (NWs), which are employed as a model material system, into functional electrochemical cells through a combination of bottom-up (dielectrophoresis) and top-down (silicon nanomachining) unit processes. The on-chip NWs are electrochemically lithiated inside a helium-filled glovebox and their electrical conductivity is studied as a function of incremental lithium loading during initial lithiation. We observe a dramatic reduction in NW conductivity (on the order of two to three orders in magnitude), which is not reversed when the lithium is extracted from the nanoelectrode. This conductivity change is attributed to an increase in lattice disorder within the material, which is observed from TEM images of the lithiated NWs. Furthermore, electron energy loss spectroscopy (EELS) was employed to confirm the reduction in valence state of manganese, which occurs due to the transformation of MnO2 to LixMnO2.

  4. Rapid charge and discharge property of high capacity lithium ion battery applying three-dimensionally patterned electrode

    NASA Astrophysics Data System (ADS)

    Izumi, Akira; Sanada, Masakazu; Furuichi, Koji; Teraki, Kuniko; Matsuda, Takeshi; Hiramatsu, Kenta; Munakata, Hirokazu; Kanamura, Kiyoshi

    2014-06-01

    The cells applied with a three-dimensionally (3D) patterned Li4Ti5O12 (LTO) electrode showed good performance as a rechargeable lithium-ion battery. The 3D-patterned electrode was fabricated with a printing apparatus and has many lined patterns with a high aspect ratio standing in line on a current collector. The cell using 3D-patterned electrode showed much better rate capability than that using a conventional flat electrode. In this research, cyclic voltammetry was carried out to investigate the mechanism realizing the high rates of charging and discharging in 3D-patterned electrode. Various types of line patterns were fabricated for 3D electrode by using LTO electrode slurry, and the influences of basic specifications of electrode structure (the space between two neighboring electrode lines, the height and width of electrode) on the charge and discharge characteristics were evaluated to optimize the electrode pattern. In addition, the electrode performance was discussed from the viewpoints of ohmic resistance and charge-transfer resistance of the cells with 3D-patterned and conventional flat electrodes.

  5. Recent achievements on inorganic electrode materials for lithium-ion batteries.

    PubMed

    Croguennec, Laurence; Palacin, M Rosa

    2015-03-11

    The lithium-ion battery technology is rooted in the studies of intercalation of guest ions into inorganic host materials developed ca. 40 years ago. It further turned into a commercial product, which will soon blow its 25th candle. Intense research efforts during this time have resulted in the development of a large spectrum of electrode materials together with deep understanding of the underlying structure-property relationships that govern their performance. This has enabled an ever increasing electrochemical yield together with the diversification of the technology into several subfamilies, tailoring materials to application requirements. The present paper aims at providing a global and critical perspective on inorganic electrode materials for lithium-ion batteries categorized by their reaction mechanism and structural dimensionality. Specific emphasis is put on recent research in the field, which beyond the chemistry and microstructure of the materials themselves also involves considering interfacial chemistry concepts alongside progress in characterization techniques. Finally a short personal perspective is provided on some plausible development of the field. PMID:25679823

  6. Rechargeable Lithium-Air Batteries: Development of Ultra High Specific Energy Rechargeable Lithium-Air Batteries Based on Protected Lithium Metal Electrodes

    SciTech Connect

    2010-07-01

    BEEST Project: PolyPlus is developing the world’s first commercially available rechargeable lithium-air (Li-Air) battery. Li-Air batteries are better than the Li-Ion batteries used in most EVs today because they breathe in air from the atmosphere for use as an active material in the battery, which greatly decreases its weight. Li-Air batteries also store nearly 700% as much energy as traditional Li-Ion batteries. A lighter battery would improve the range of EVs dramatically. Polyplus is on track to making a critical breakthrough: the first manufacturable protective membrane between its lithium–based negative electrode and the reaction chamber where it reacts with oxygen from the air. This gives the battery the unique ability to recharge by moving lithium in and out of the battery’s reaction chamber for storage until the battery needs to discharge once again. Until now, engineers had been unable to create the complex packaging and air-breathing components required to turn Li-Air batteries into rechargeable systems.

  7. Electrochemical properties of an all-solid-state lithium-ion battery with an in-situ formed electrode material grown from a lithium conductive glass ceramics sheet

    NASA Astrophysics Data System (ADS)

    Amiki, Yuichi; Sagane, Fumihiro; Yamamoto, Kazuo; Hirayama, Tsukasa; Sudoh, Masao; Motoyama, Munekazu; Iriyama, Yasutoshi

    2013-11-01

    A lithium insertion reaction in a Li+ conductive glass ceramics solid electrolyte (lithium aluminum titanium phosphate: LATP) sheet produces an in-situ formed electrode active material, which operates at 2.35 V vs. Li/Li+ in the vicinity of the LATP-sheet/current-collector interface. Electron energy loss spectroscopy clarifies that titanium in the LATP sheet in the vicinity of the current collector/LATP-sheet interface is preferentially reduced by this lithium insertion reaction. Charge transfer resistance between the in-situ-formed-electrode and the LATP-sheet is less than 100 Ω cm2, which is smaller than that of the common LiPON/LiCoO2 interface. A thin film of LiCoO2 is deposited on one side of the LATP-sheet as a Li+ source for developing the in-situ formed electrode material. Eventually, a Pt/LATP-sheet/LiCoO2/Au multilayer is fabricated. The multilayer structure successfully works as an all-solid-state lithium-ion battery operating at 1.5 V. A redox peak of the battery is observed even at 100 mV s-1 in the potential sweep curve. Additionally, charge-discharge reactions are repeated stably even after 25 cycles.

  8. Lithium wall conditioning and surface dust detection on NSTX, and dust removal

    SciTech Connect

    Skinner, C. H.; Allain, J. P.; Bell, M. G.; Friesen, F. Q.L.; Helm, B.; Jaworski, M. A.; Kugel, H.; Maingi, R.; Rais, B.; Taylor, C. N.

    2011-01-01

    Lithium evaporation onto National Spherical Torus Experiment (NSTX) plasma-facing components (PFCs) has resulted in improved energy confinement, and reductions in the number and amplitude of edge-localized modes (ELMs) up to the point of complete ELM suppression. The associated PFC surface chemistry has been investigated with a novel plasma-material interface probe connected to an in-vacuo surface analysis station. Analysis has demonstrated that the binding of D atoms to the polycrystalline graphite material of PFCs is fundamentally changed by lithium-in particular, deuterium atoms become weakly bonded near lithium atoms themselves bound to either oxygen or the carbon from the underlying material. Surface dust inside NSTX has been detected in real time using a highly sensitive electrostatic dust detector. In a separate experiment, electrostatic removal of dust via three concentric spiral-shaped electrodes covered by a dielectric and driven by a high-voltage three-phase waveform was evaluated for its potential application to fusion reactors.

  9. Surface modifications for carbon lithium intercalation anodes

    DOEpatents

    Tran, Tri D.; Kinoshita, Kimio

    2000-01-01

    A prefabricated carbon anode containing predetermined amounts of passivating film components is assembled into a lithium-ion rechargeable battery. The modified carbon anode enhances the reduction of the irreversible capacity loss during the first discharge of a cathode-loaded cell. The passivating film components, such as Li.sub.2 O and Li.sub.2 CO.sub.3, of a predetermined amount effective for optimal passivation of carbon, are incorporated into carbon anode materials to produce dry anodes that are essentially free of battery electrolyte prior to battery assembly.

  10. Surface Chemistry and Precursor Material Effects on the Performance of Pyrolyzed Nanofibers as Anodes for Lithium-ion Batteries

    NASA Astrophysics Data System (ADS)

    Loebl, Andrew James

    Next-generation lithium-ion batteries to meet consumer demands and new applications require the development of new electrode materials. Electrospinning of polymers is a simple and effective method to create one-dimensional, self-supporting materials, with no inactive components after pyrolysis. Composites of these nanofibers and high-capacity lithium materials have been demonstrated to possess superior reversible capacity than state-of-the-art commercial anodes. Despite impressive reversible discharge capacities polyacrylonitrile-based composites are not ready for adoption in commercial applications. These materials suffer from irreversible losses of Li to formation on the electrode of the solid electrolyte interphase during the first charge of the cell. This thesis work has taken two approaches to engineer high-performing nanofiber-based electrodes. First, the chemistry at the interface of the electrode and the electrolyte has been changed by depositing new surfaces. Attempts to create a graphitic fiber surface via plasma enhanced chemical vapor deposition did not result in an improvement of the irreversible losses. However, the experiments did demonstrate the growth of large surface area carbon nanowalls on the pyrolyzed electrospun fibers, creating a material which could serve as a substrate in catalysis or as an electrode for composite ultra-capacitors. Additionally, passivation surfaces were deposited by atomic layer deposition and molecular layer deposition. These new surfaces were employed to reduce the irreversible consumption of lithium by moving the charge transfer reaction to the interface of the carbon and the new material. The removal the lithium from the solvent prior to charge transfer limits the irreversible reduction of solvent by metallic lithium. Alumina films grown by atomic layer deposition reduced lithium losses to the solid electrolyte interphase by up to 42% for twenty deposition cycles. This large improvement in irreversible capacity

  11. In situ and operando atomic force microscopy of high-capacity nano-silicon based electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Breitung, Ben; Baumann, Peter; Sommer, Heino; Janek, Jürgen; Brezesinski, Torsten

    2016-07-01

    Silicon is a promising next-generation anode material for high-energy-density lithium-ion batteries. While the alloying of nano- and micron size silicon with lithium is relatively well understood, the knowledge of mechanical degradation and structural rearrangements in practical silicon-based electrodes during operation is limited. Here, we demonstrate, for the first time, in situ and operando atomic force microscopy (AFM) of nano-silicon anodes containing polymer binder and carbon black additive. With the help of this technique, the surface topography is analyzed while electrochemical reactions are occurring. In particular, changes in particle size as well as electrode structure and height are visualized with high resolution. Furthermore, the formation and evolution of the solid-electrolyte interphase (SEI) can be followed and its thickness determined by phase imaging and nano-indentation, respectively. Major changes occur in the first lithiation cycle at potentials below 0.6 V with respect to Li/Li+ due to increased SEI formation - which is a dynamic process - and alloying reactions. Overall, these results provide insight into the function of silicon-based composite electrodes and further show that AFM is a powerful technique that can be applied to important battery materials, without restriction to thin film geometries.Silicon is a promising next-generation anode material for high-energy-density lithium-ion batteries. While the alloying of nano- and micron size silicon with lithium is relatively well understood, the knowledge of mechanical degradation and structural rearrangements in practical silicon-based electrodes during operation is limited. Here, we demonstrate, for the first time, in situ and operando atomic force microscopy (AFM) of nano-silicon anodes containing polymer binder and carbon black additive. With the help of this technique, the surface topography is analyzed while electrochemical reactions are occurring. In particular, changes in particle

  12. Comparison of H-Mode Plasmas Diverted to Solid and Liquid Lithium Surfaces

    SciTech Connect

    R. Kaita, et. al.

    2012-07-20

    Experiments were conducted with a Liquid Lithium Divertor (LLD) in NSTX. Among the goals was to use lithium recoating to sustain deuterium (D) retention by a static liquid lithium surface, approximating the ability of flowing liquid lithium to maintain chemical reactivity. Lithium evaporators were used to deposit lithium on the LLD surface. Improvements in plasma edge conditions were similar to those with lithiated graphite plasma-facing components (PFCs), including an increase in confinement over discharges without lithiumcoated PFCs and ELM reduction during H-modes. With the outer strike point on the LLD, the D retention in the LLD was about the same as that for solid lithium coatings on graphite, or about two times that achieved without lithium PFC coatings. There were also indications of contamination of the LLD surface, possibly due erosion and redeposition of carbon from PFCs. Flowing lithium may thus be needed for chemically active PFCs during long-pulse operation.

  13. Li(V0.5Ti0.5)S2 as a 1 V lithium intercalation electrode

    PubMed Central

    Clark, Steve J.; Wang, Da; Armstrong, A. Robert; Bruce, Peter G.

    2016-01-01

    Graphite, the dominant anode in rechargeable lithium batteries, operates at ∼0.1 V versus Li+/Li and can result in lithium plating on the graphite surface, raising safety concerns. Titanates, for example, Li4Ti5O12, intercalate lithium at∼1.6 V versus Li+/Li, avoiding problematic lithium plating at the expense of reduced cell voltage. There is interest in 1 V anodes, as this voltage is sufficiently high to avoid lithium plating while not significantly reducing cell potential. The sulfides, LiVS2 and LiTiS2, have been investigated as possible 1 V intercalation electrodes but suffer from capacity fading, large 1st cycle irreversible capacity or polarization. Here we report that the 50/50 solid solution, Li1+x(V0.5Ti0.5)S2, delivers a reversible capacity to store charge of 220 mAhg−1 (at 0.9 V), 99% of theoretical, at a rate of C/2, retaining 205 mAhg−1 at C-rate (92% of theoretical). Rate capability is excellent with 200 mAhg−1 at 3C. C-rate is discharge in 1 h. Polarization is low, 100 mV at C/2. To the best of our knowledge, the properties/performances of Li(V0.5Ti0.5)S2 exceed all previous 1 V electrodes. PMID:26996753

  14. Li(V0.5Ti0.5)S2 as a 1 V lithium intercalation electrode.

    PubMed

    Clark, Steve J; Wang, Da; Armstrong, A Robert; Bruce, Peter G

    2016-01-01

    Graphite, the dominant anode in rechargeable lithium batteries, operates at ∼0.1 V versus Li(+)/Li and can result in lithium plating on the graphite surface, raising safety concerns. Titanates, for example, Li4Ti5O12, intercalate lithium at∼1.6 V versus Li(+)/Li, avoiding problematic lithium plating at the expense of reduced cell voltage. There is interest in 1 V anodes, as this voltage is sufficiently high to avoid lithium plating while not significantly reducing cell potential. The sulfides, LiVS2 and LiTiS2, have been investigated as possible 1 V intercalation electrodes but suffer from capacity fading, large 1st cycle irreversible capacity or polarization. Here we report that the 50/50 solid solution, Li1+x(V0.5Ti0.5)S2, delivers a reversible capacity to store charge of 220 mAhg(-1) (at 0.9 V), 99% of theoretical, at a rate of C/2, retaining 205 mAhg(-1) at C-rate (92% of theoretical). Rate capability is excellent with 200 mAhg(-1) at 3C. C-rate is discharge in 1 h. Polarization is low, 100 mV at C/2. To the best of our knowledge, the properties/performances of Li(V0.5Ti0.5)S2 exceed all previous 1 V electrodes. PMID:26996753

  15. Lithium

    USGS Publications Warehouse

    Jaskula, B.W.

    2011-01-01

    In 2010, lithium consumption in the United States was estimated to have been about 1 kt (1,100 st) of contained lithium, a 23-percent decrease from 2009. The United States was estimated to be the fourth largest consumer of lithium. It remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. Only one company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic resources. In 2010, world lithium consumption was estimated to have been about 21 kt (22,000 st) of lithium contained in minerals and compounds, a 12-percent increase from 2009.

  16. Lithium

    USGS Publications Warehouse

    Jaskula, B.W.

    2010-01-01

    In 2009, lithium consumption in the United States was estimated to have been about 1.2 kt (1,300 st) of contained lithium, a 40-percent decrease from 2008. The United States was estimated to be the fourth largest consumer of lithium, and remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. Only one company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic resources. In 2009, world lithium consumption was estimated to have been about 18.7 kt (20,600 st) of lithium contained in minerals and compounds.

  17. Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery. M.S. Thesis

    NASA Technical Reports Server (NTRS)

    Nicholson, Marjorie Anne

    1991-01-01

    A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

  18. Fabrication of Binder-Free Pencil-Trace Electrode for Lithium-Ion Battery: Simplicity and High Performance.

    PubMed

    Park, Hyean-Yeol; Kim, Min-Sik; Bae, Tae-Sung; Yuan, Jinliang; Yu, Jong-Sung

    2016-05-10

    A binder-free and solvent-free pencil-trace electrode with intercalated clay particles (mainly SiO2) is prepared via a simple pencil-drawing process on grinded Cu substrate with rough surface and evaluated as an anode material for lithium-ion battery. The pencil-trace electrode exhibits a high reversible capacity of 672 mA h g(-1) at 100 mA g(-1) after 100 cycles, which can be attributed to the unique multilayered graphene particles with lateral size of few micrometers and the formation of LixSi alloys generated by interaction between Li(+) and an active Si produced in the electrochemical reduction of nano-SiO2 in the clay particles between the multilayered graphene particles. The multilayered graphene obtained by this process consists of 1 up to 20 and occasionally up to 50 sheets and thus can not only help accommodating the volume change and alleviating the structural strain during Li ion insertion and extraction but also allow rapid access of Li ions during charge-discharge cycling. Drawing with a pencil on grinded Cu substrate is not only very simple but also cost-effective and highly scalable, easily establishing graphitic circuitry through a solvent-free and binder-free approach. PMID:27082026

  19. Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes

    SciTech Connect

    Wang, Feng; Robert, Rosa; Chernova, Natasha A.; Pereira, Nathalie; Omenya, Fredrick; Badway, Fadwa; Hua, Xiao; Ruotolo, Michael; Zhang, Ruigang; Wu, Lijun; Volkov, Vyacheslav; Su, Dong; Key, Baris; Whittingham, M. Stanley; Grey, Clare P.; Amatucci, Glenn G.; Zhu, Yimei; Graetz, Jason

    2015-10-15

    Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF{sub 2}: M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF{sub 2}) while others are not (e.g., CuF{sub 2}). In this study, we investigated the conversion reaction of binary metal fluorides, FeF{sub 2} and CuF{sub 2}, using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF{sub 2} and CuF{sub 2} react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li{sup +} with FeF{sub 2}, small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF{sub 2}. In contrast

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

    PubMed

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H; Polzin, Bryant J; Wang, Chongmin; Zhang, Ji-Guang; Xu, Wu

    2016-03-01

    The effects of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite∥LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs(+) additive. The synergistic effects of Cs(+) additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li(+) ions and allows fast Li(+) ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite∥NCA full cells under a wide temperature range. The fundamental findings also shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices. PMID:26862677

  1. Polyanthraquinone as a Reliable Organic Electrode for Stable and Fast Lithium Storage.

    PubMed

    Song, Zhiping; Qian, Yumin; Gordin, Mikhail L; Tang, Duihai; Xu, Terrence; Otani, Minoru; Zhan, Hui; Zhou, Haoshen; Wang, Donghai

    2015-11-16

    In spite of recent progress, there is still a lack of reliable organic electrodes for Li storage with high comprehensive performance, especially in terms of long-term cycling stability. Herein, we report an ideal polymer electrode based on anthraquinone, namely, polyanthraquinone (PAQ), or specifically, poly(1,4-anthraquinone) (P14AQ) and poly(1,5-anthraquinone) (P15AQ). As a lithium-storage cathode, P14AQ showed exceptional performance, including reversible capacity almost equal to the theoretical value (260 mA h g(-1); >257 mA h g(-1) for AQ), a very small voltage gap between the charge and discharge curves (2.18-2.14=0.04 V), stable cycling performance (99.4% capacity retention after 1000 cycles), and fast-discharge/charge ability (release of 69% of the low-rate capacity or 64% of the energy in just 2 min). Exploration of the structure-performance relationship between P14AQ and related materials also provided us with deeper understanding for the design of organic electrodes. PMID:26411505

  2. Interactions between organic additives and active powders in water-based lithium iron phosphate electrode slurries

    NASA Astrophysics Data System (ADS)

    Li, Chia-Chen; Lin, Yu-Sheng

    2012-12-01

    The interactions of organic additives with active powders are investigated and are found to have great influence on the determination of the mixing process for preparing electrode slurries with good dispersion and electrochemical properties of lithium iron phosphate (LiFePO4) electrodes. Based on the analyses of zeta potential, sedimentation, and rheology, it is shown that LiFePO4 prefers to interact with styrene-butadiene rubber (SBR) relative to other organic additives such as sodium carboxymethyl cellulose (SCMC), and thus shows preferential adsorption by SBR, whereas SBR has much lower efficiency than SCMC in dispersing LiFePO4. Therefore, for SCMC to interact with and disperse LiFePO4 before the interaction of LiFePO4 with SBR, it is suggested to mix SCMC with LiFePO4 prior to the addition of SBR during the slurry preparation process. For the electrode prepared via the suggested process, i.e., the sequenced adding process in which SCMC is mixed with active powders prior to the addition of SBR, a much better electrochemical performance is obtained than that of the one prepared via the process referred as the simultaneous adding process, in which mixing of SCMC and SBR with active powders in simultaneous.

  3. Pie-like electrode design for high-energy density lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Li, Zhen; Zhang, Jin Tao; Chen, Yu Ming; Li, Ju; Lou, Xiong Wen (David)

    2015-11-01

    Owing to the overwhelming advantage in energy density, lithium-sulfur (Li-S) battery is a promising next-generation electrochemical energy storage system. Despite many efforts in pursuing long cycle life, relatively little emphasis has been placed on increasing the areal energy density. Herein, we have designed and developed a `pie' structured electrode, which provides an excellent balance between gravimetric and areal energy densities. Combining lotus root-like multichannel carbon nanofibers `filling' and amino-functionalized graphene `crust', the free-standing paper electrode (S mass loading: 3.6 mg cm-2) delivers high specific capacity of 1,314 mAh g-1 (4.7 mAh cm-2) at 0.1 C (0.6 mA cm-2) accompanied with good cycling stability. Moreover, the areal capacity can be further boosted to more than 8 mAh cm-2 by stacking three layers of paper electrodes with S mass loading of 10.8 mg cm-2.

  4. Graphene protected surface state on Ir(111) with adsorbed lithium

    NASA Astrophysics Data System (ADS)

    Lazic, Predrag; Pervan, Petar; Petrovic, Marin; Srut-Rakic, Iva; Pletikosic, Ivo; Kralj, Marko; Milun, Milorad; Valla, Tonica

    It is well known that electronic surface states (SS) get strongly perturbed upon the chemical adsorption of very small amount of adsorbates. Adsorption of lithium atoms on Ir(111) is no exception to that rule. Iridium SS gets strongly perturbed and is practically eradicated - it can not be seen as a sharp peak in the ARPES measurement. However, if the system is prepared with graphene on top of Ir/Li system, the iridium SS reappears. We present a combined experimental and theoretical study of the described system. Using the density functional theory calculations for large unit cells with disordered lithium atoms geometries on the (111) surface of iridium we were able to reproduce the results of the ARPES measurements - showing clearly that the SS signal is strongly suppressed when lithium is adsorbed, while it is almost unchanged when lithium is intercalated (i.e. with graphene on top of it). Looking at the projected density of states we constructed a rather simple model explaining this behavior which seems to be general.

  5. Comparison of three-dimensional analysis and stereological techniques for quantifying lithium-ion battery electrode microstructures.

    PubMed

    Taiwo, Oluwadamilola O; Finegan, Donal P; Eastwood, David S; Fife, Julie L; Brown, Leon D; Darr, Jawwad A; Lee, Peter D; Brett, Daniel J L; Shearing, Paul R

    2016-09-01

    Lithium-ion battery performance is intrinsically linked to electrode microstructure. Quantitative measurement of key structural parameters of lithium-ion battery electrode microstructures will enable optimization as well as motivate systematic numerical studies for the improvement of battery performance. With the rapid development of 3-D imaging techniques, quantitative assessment of 3-D microstructures from 2-D image sections by stereological methods appears outmoded; however, in spite of the proliferation of tomographic imaging techniques, it remains significantly easier to obtain two-dimensional (2-D) data sets. In this study, stereological prediction and three-dimensional (3-D) analysis techniques for quantitative assessment of key geometric parameters for characterizing battery electrode microstructures are examined and compared. Lithium-ion battery electrodes were imaged using synchrotron-based X-ray tomographic microscopy. For each electrode sample investigated, stereological analysis was performed on reconstructed 2-D image sections generated from tomographic imaging, whereas direct 3-D analysis was performed on reconstructed image volumes. The analysis showed that geometric parameter estimation using 2-D image sections is bound to be associated with ambiguity and that volume-based 3-D characterization of nonconvex, irregular and interconnected particles can be used to more accurately quantify spatially-dependent parameters, such as tortuosity and pore-phase connectivity. PMID:26999804

  6. Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes.

    PubMed

    Li, Linsen; Jacobs, Ryan; Gao, Peng; Gan, Liyang; Wang, Feng; Morgan, Dane; Jin, Song

    2016-03-01

    Metal fluorides and oxides can store multiple lithium ions through conversion chemistry to enable high-energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage profiles and the consequent low-energy efficiency (<80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the FeF3 electrode is kinetic in nature. It is the result of ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically active phases (i.e., compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry. PMID:26847657

  7. Multiscale modeling of lithium-ion battery electrodes based on nano-scale X-ray computed tomography

    NASA Astrophysics Data System (ADS)

    Kashkooli, Ali Ghorbani; Farhad, Siamak; Lee, Dong Un; Feng, Kun; Litster, Shawn; Babu, Siddharth Komini; Zhu, Likun; Chen, Zhongwei

    2016-03-01

    A multiscale platform has been developed to model lithium ion battery (LIB) electrodes based on the real microstructure morphology. This multiscale framework consists of a microscale level where the electrode microstructure architecture is modeled and a macroscale level where discharge/charge is simulated. The coupling between two scales are performed in real time unlike using common surrogate based models for microscale. For microscale geometry 3D microstructure is reconstructed based on the nano-scale X-ray computed tomography data replacing typical computer generated microstructure. It is shown that this model can predict the experimental performance of LiFePO4 (LFP) cathode at different discharge rates more accurate than the conventional homogenous models. The approach employed in this study provides valuable insight into the spatial distribution of lithium -ion inside the real microstructure of LIB electrodes. The inhomogenous microstructure of LFP causes a wider range of physical and electrochemical properties in microscale compared to homogenous models.

  8. Lithium

    USGS Publications Warehouse

    Jaskula, B.W.

    2012-01-01

    In 2011, world lithium consumption was estimated to have been about 25 kt (25,000 st) of lithium contained in minerals and compounds, a 10-percent increase from 2010. U.S. consumption was estimated to have been about 2 kt (2,200 st) of contained lithium, a 100-percent increase from 2010. The United States was estimated to be the fourth-ranked consumer of lithium and remained the leading importer of lithium carbonate and the leading producer of value-added lithium materials. One company, Chemetall Foote Corp. (a subsidiary of Chemetall GmbH of Germany), produced lithium compounds from domestic brine resources near Silver Peak, NV.

  9. MoS2/C Multilayer Nanospheres as an Electrode Base for Lithium Power Sources.

    PubMed

    Shyyko, Lyudmyla O; Kotsyubynsky, Volodymyr O; Budzulyak, Ivan M; Sagan, Piotr

    2016-12-01

    Multilayer nanospheres with alternating 2H-MoS2 and C layers were studied as a cathode base for lithium power sources. Interesting hierarchical structure, synergetic effect, and the presence of defects as supplementary active sites, introduced by the additional annealing at 773 K in Ar atmosphere, have determined the conductivity, referred to symmetric hopping or random barrier model, and led to achieve the high values of specific capacity of 3700, 1390, and 790 A h kg(-1) at currents 0.1, 0.3, and 0.5 C. Such unusual result was never reported before and could be explained by combining of the faradaic and non-faradaic accumulation processes within electrode material. PMID:27146144

  10. MoS2/C Multilayer Nanospheres as an Electrode Base for Lithium Power Sources

    NASA Astrophysics Data System (ADS)

    Shyyko, Lyudmyla O.; Kotsyubynsky, Volodymyr O.; Budzulyak, Ivan M.; Sagan, Piotr

    2016-05-01

    Multilayer nanospheres with alternating 2H-MoS2 and C layers were studied as a cathode base for lithium power sources. Interesting hierarchical structure, synergetic effect, and the presence of defects as supplementary active sites, introduced by the additional annealing at 773 K in Ar atmosphere, have determined the conductivity, referred to symmetric hopping or random barrier model, and led to achieve the high values of specific capacity of 3700, 1390, and 790 A h kg-1 at currents 0.1, 0.3, and 0.5 C. Such unusual result was never reported before and could be explained by combining of the faradaic and non-faradaic accumulation processes within electrode material.

  11. Evaluation and Testing of Commercially-Available Carbon Nanotubes as Negative Electrodes for Lithium Ion Cells

    NASA Technical Reports Server (NTRS)

    Britton, Doris L.

    2007-01-01

    Rechargeable lithium ion (Li-ion) battery technology offers significant performance advantages over the nickel-based technologies used for energy storage for the majority of NASA's missions. Specifically Li-ion technology offers a threefold to fourfold increase in gravimetric and volumetric energy densities and produces voltages in excess of three times the value of typical nickel-based battery systems. As part of the Advanced Battery Technology program at NASA Glenn Research Center (GRC), a program on the evaluation of anodes for Li-ion cells and batteries was conducted. This study focused on the feasibility of using carbon nanotubes as anodes in Li-Ion cells. Candidate materials from multiple sources were evaluated. Their performance was compared to a standard anode comprised of mesocarbon microbeads. In all cases, the standard MCMB electrode exhibited superior performance. The details and results of the study are presented.

  12. Room temperature performance of 4 V aqueous hybrid supercapacitor using multi-layered lithium-doped carbon negative electrode

    NASA Astrophysics Data System (ADS)

    Makino, Sho; Yamamoto, Rie; Sugimoto, Shigeyuki; Sugimoto, Wataru

    2016-09-01

    Water-stable multi-layered lithium-doped carbon (LixC6) negative electrode using poly(ethylene oxide) (PEO)-lithium bis(trifluoromethansulfonyl)imide (LiTFSI) polymer electrolyte containing N-methyl-N-propylpiperidinium bis(trifluoromethansulfonyl)imide (PP13TFSI) ionic liquid was developed. Electrochemical properties at 60 °C of the aqueous hybrid supercapacitor using activated carbon positive electrode and a multi-layered LixC6 negative electrode (LixC6 | PEO-LiTFSI | LTAP) without PP13TFSI exhibited performance similar to that using Li anode (Li | PEO-LiTFSI | LTAP). A drastic decrease in ESR was achieved by the addition of PP13TFSI to PEO-LiTFSI, allowing room temperature operation. The ESR of the multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C was 801 Ω cm2, which is 1/6 the value of the multi-layered Li negative electrode with PEO-LiTFSI (5014 Ω cm2). Charge/discharge test of the aqueous hybrid supercapacitor using multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI at 25 °C afforded specific capacity of 20.6 mAh (g-activated carbon)-1 with a working voltage of 2.7-3.7 V, and good long-term capability up to 3000 cycles. Furthermore, an aqueous hybrid supercapacitor consisting of a high capacitance RuO2 nanosheet positive electrode and multi-layered LixC6 negative electrode with PEO-LiTFSI-PP13TFSI showed specific capacity of 196 mAh (g-RuO2)-1 and specific energy of 625 Wh (kg-RuO2)-1 in 2.0 M acetic acid-lithium acetate buffered solution at 25 °C.

  13. Layered manganese oxide intergrowth electrodes for rechargeable lithium batteries: Part 1-substitution with Co or Ni

    SciTech Connect

    Dolle, Mickael; Patoux, Sebastien; Doeff, Marca M.

    2004-09-08

    Lithium manganese oxides substituted with nickel or cobalt were characterized electrochemically in lithium cell configurations. The compounds studied were either single-phase layered structures with either primarily O2 or O3 stacking arrangements, or O2/O3 intergrowths, prepared from P2, P3 and P2/P3 sodium-containing precursors, respectively. The stacking arrangements are extremely sensitive to the Na/T. M. (T. M. = transition metal) ratios and the level of substitution. Phase diagrams showing the stability regions of the various arrangements for the Na-Ni-Mn-O system are presented. A possible correlation between vacancies and electrochemical performance is suggested. For high levels of substitution with Ni, fewer defects are possible for materials containing more O3 component and higher discharge capacities can be achieved, but spinel conversion upon cycling also occurs more rapidly as the O3 content increases. Intergrowths show intermediate behavior and represent a potential route towards designing stable, high capacity electrodes.

  14. Real-Time NMR Investigations of Structural Changes in Silicon Electrodes for Lithium-Ion Batteries

    SciTech Connect

    Key, Baris; Bhattacharyya, Rangeet; Morcrette, Mathieu; Seznec, Vincent; Tarascon, Jean-Marie; Grey, Clare P.

    2009-12-10

    Lithium-ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation because of the extremely large gravimetric and volumetric capacity of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attempts to link structure in these systems with electrochemical performance. We apply a combination of static, in situ and magic angle sample spinning, ex situ {sup 7}Li nuclear magnetic resonance (NMR) studies to investigate the changes in local structure that occur in an actual working LIB. The first discharge occurs via the formation of isolated Si atoms and smaller Si-Si clusters embedded in a Li matrix; the latter are broken apart at the end of the discharge, forming isolated Si atoms. A spontaneous reaction of the lithium silicide with the electrolyte is directly observed in the in situ NMR experiments; this mechanism results in self-discharge and potential capacity loss. The rate of this self-discharge process is much slower when CMC (carboxymethylcellulose) is used as the binder.

  15. Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries.

    PubMed

    Key, Baris; Bhattacharyya, Rangeet; Morcrette, Mathieu; Seznéc, Vincent; Tarascon, Jean-Marie; Grey, Clare P

    2009-07-01

    Lithium-ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation because of the extremely large gravimetric and volumetric capacity of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attempts to link structure in these systems with electrochemical performance. We apply a combination of static, in situ and magic angle sample spinning, ex situ (7)Li nuclear magnetic resonance (NMR) studies to investigate the changes in local structure that occur in an actual working LIB. The first discharge occurs via the formation of isolated Si atoms and smaller Si-Si clusters embedded in a Li matrix; the latter are broken apart at the end of the discharge, forming isolated Si atoms. A spontaneous reaction of the lithium silicide with the electrolyte is directly observed in the in situ NMR experiments; this mechanism results in self-discharge and potential capacity loss. The rate of this self-discharge process is much slower when CMC (carboxymethylcellulose) is used as the binder. PMID:19298062

  16. Multi-band reflectance spectroscopy of carbonaceous lithium iron phosphate battery electrodes versus state of charge

    NASA Astrophysics Data System (ADS)

    Norris, R.; Iyer, K.; Chabot, V.; Nieva, P.; Yu, A.; Khajepour, A.; Wang, J.

    2014-03-01

    This study aims to expand the body of knowledge about the optical properties of battery cathode materials. Although some studies have been conducted on the optical properties of Lithium Iron Phosphate (LiFePO4), to the authors' knowledge, this is the first study of its kind on electrodes extracted from commercially available LiFePO4 batteries. The use of Vis/NIR and FTIR spectroscopy provides for a methodology to study the optical properties of LiFePO4 and may allow for the characterization of other properties such as particle size and the proportions of LiFePO4 versus FePO4 material. Knowledge of these properties is important for the development of a mechanism to measure the state-of charge (SOC) in lithium ion batteries. These properties are also important in a host of other applications including battery modeling and materials characterization. Cylindrical LiFePO4 batteries (from A123 Systems Inc.) were acquired from the commercial market and charged to 10 different states between 30% and 80% of their nominal capacity using a constant-current, constant-voltage (CCCV) cycling method. Visual inspection of the extracted electrodes shows that the LiFePO4/C-cathodes display subtle changes in color (shades of grey) with respect to SOC. Vis/NIR measurements support the visual observation of uniform intensity variations versus SOC. FTIR measurements show an absorbance signature that varies with SOC and is distinct from results found in the literature for similar LiFePO4-based material systems, supporting the uniqueness of the absorbance fingerprint.

  17. Lithium

    USGS Publications Warehouse

    Ober, J.A.

    2006-01-01

    In 2005, lithium consumption in the United States was at 2.5 kt of contained lithium, nearly 32% more than the estimate for 2004. World consumption was 14.1 kt of lithium contained in minerals and compounds in 2003. Exports from the US increased slightly compared with 2004. Due to strong demand for lithium compounds in 2005, both lithium carbonate plants in Chile were operating at or near capacity.

  18. Factors determining the packing-limitation of active materials in the composite electrode of lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kitada, Koji; Murayama, Haruno; Fukuda, Katsutoshi; Arai, Hajime; Uchimoto, Yoshiharu; Ogumi, Zempachi; Matsubara, Eiichiro

    2016-01-01

    The factors limiting the capacity of highly dense electrodes are elucidated by using composite electrodes for lithium-ion batteries, which consist of active materials LiNi1/3Co1/3Mn1/3O2 (NCM), conductive additives and binders. Electrochemical tests of such 100-μm-thick electrodes in 1 M LiPF6 electrolyte indicate that a highly dense electrode (with 18% porosity) shows a capacity density significantly lower than the other sparse electrodes on 1C charging/discharging. Detailed analysis using position sensitive in situ X-ray diffraction indicates that, unlike the other sparse electrodes, NCM on the current-collector side barely functions for this dense electrode, due to the poor accessibility of Li+ to the inner part of the electrode. Interestingly, 2 M and 0.3 M electrolytes promote the discharge and charge reactions, respectively, over the entire area of the electrode, although they exhibit lower conductivity than the 1 M electrolyte, which indicates the importance of the initial amount of Li+ in the electrolyte impregnated in the electrode pores. Thus, for a high-energy-density cell, the initial amount of Li+ and the Li+ transport significantly affect the rate capability, which governs the practical capacity of the cell under constant-current operation.

  19. Lithium orthosilicate surfaces: Characterization and effect on tritium release

    NASA Astrophysics Data System (ADS)

    Kolb, M. H. H.; Bruns, M.; Knitter, R.; van Til, S.

    2012-08-01

    Within the European Union, slightly hyperstoichiometric lithium orthosilicate has evolved as one of the candidate solid breeder materials for the helium cooled pebble bed blanket, which will be tested in ITER. In the past, several long-term irradiation experiments proved that lithium orthosilicate shows excellent tritium release behavior when purged with helium with 0.1% hydrogen. In this work, short-term irradiation experiments at the High Flux Reactor in Petten with two standard pebble qualities, as-received and heat-treated lithium orthosilicate were carried out to investigate possible differences in tritium release. Since the surface of the pebbles may play a significant role, especially for short-term irradiation, and the mechanism of desorption from the surface determines the chemical form and very likely the release rate of tritium, the aim of this work is to link the chemical composition of the surface to the Thermal Programmed Desorption (TPD) tritium release experiments. Therefore X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were applied to characterize the surface of the unirradiated pebbles and to obtain sputter depth profiles of up to 800 nm. In addition, X-ray diffractometry was used to determine the composition of phases of the samples before and after irradiation.

  20. Surface modification of active material structures in battery electrodes

    DOEpatents

    Erickson, Michael; Tikhonov, Konstantin

    2016-02-02

    Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

  1. In situ and operando atomic force microscopy of high-capacity nano-silicon based electrodes for lithium-ion batteries.

    PubMed

    Breitung, Ben; Baumann, Peter; Sommer, Heino; Janek, Jürgen; Brezesinski, Torsten

    2016-08-01

    Silicon is a promising next-generation anode material for high-energy-density lithium-ion batteries. While the alloying of nano- and micron size silicon with lithium is relatively well understood, the knowledge of mechanical degradation and structural rearrangements in practical silicon-based electrodes during operation is limited. Here, we demonstrate, for the first time, in situ and operando atomic force microscopy (AFM) of nano-silicon anodes containing polymer binder and carbon black additive. With the help of this technique, the surface topography is analyzed while electrochemical reactions are occurring. In particular, changes in particle size as well as electrode structure and height are visualized with high resolution. Furthermore, the formation and evolution of the solid-electrolyte interphase (SEI) can be followed and its thickness determined by phase imaging and nano-indentation, respectively. Major changes occur in the first lithiation cycle at potentials below 0.6 V with respect to Li/Li(+) due to increased SEI formation - which is a dynamic process - and alloying reactions. Overall, these results provide insight into the function of silicon-based composite electrodes and further show that AFM is a powerful technique that can be applied to important battery materials, without restriction to thin film geometries. PMID:27222212

  2. Surface-enhanced Raman spectroscopy of surfactants on silver electrodes

    SciTech Connect

    Sun, Soncheng; Birke, R.L.; Lombardi, J.R. )

    1990-03-08

    Surface-enhanced Raman spectroscopy (SERS) has been used to study different kinds of surfactants (cationic, anionic, and nonionic surfactants) adsorbed on a roughened Ag electrode. Spectral assignments are made for the SERS spectrum of cetylpyridinium chloride (CPC), and it is shown that the molecule is oriented with its pyridinium ring end-on at the electrode surface at potentials positive to the point of zero charge (pzc) on Ag.

  3. Effect of Energetic Plasma Flux on Flowing Liquid Lithium Surfaces

    NASA Astrophysics Data System (ADS)

    Kalathiparambil, Kishor; Jung, Soonwook; Christenson, Michael; Fiflis, Peter; Xu, Wenyu; Szott, Mathew; Ruzic, David

    2014-10-01

    An operational liquid lithium system with steady state flow driven by thermo-electric magneto-hydrodynamic force and capable of constantly refreshing the plasma exposed surface have been demonstrated at U of I. To evaluate the system performance in reactor relevant conditions, specifically to understand the effect of disruptive plasma events on the performance of the liquid metal PFCs, the setup was integrated to a pulsed plasma generator. A coaxial plasma generator drives the plasma towards a theta pinch which preferentially heats the ions, simulating ELM like flux, and the plasma is further guided towards the target chamber which houses the flowing lithium system. The effect of the incident flux is examined using diagnostic tools including triple Langmuir probe, calorimeter, rogowski coils, Ion energy analyzers, and fast frame spectral image acquisition with specific optical filters. The plasma have been well characterized and a density of ~1021 m-3, with electron temperature ~10 - 20 eV is measured, and final plasma velocities of 34 - 74 kms-1 have been observed. Calorimetric measurements using planar molybdenum targets indicate a maximum plasma energy (with 6 kV plasma gun and 20 kV theta pinch) of 0.08 MJm-2 with plasma divergence effects resulting in marginal reduction of 40 +/- 23 J in plasma energy. Further results from the other diagnostic tools, using the flowing lithium targets and the planar targets coated with lithium will be presented. DOE DE-SC0008587.

  4. Electrode structure and method for making the same

    SciTech Connect

    Affinito, John D.; Lowe, Gregory K.

    2015-05-26

    Electrode structures, and more specifically, electrode structures for use in electrochemical cells, are provided. The electrode structures described herein may include one or more protective layers. In one set of embodiments, a protective layer may be formed by exposing a lithium metal surface to a plasma comprising ions of a gas to form a ceramic layer on top of the lithium metal. The ceramic layer may be highly conductive to lithium ions and may protect the underlying lithium metal surface from reaction with components in the electrolyte. In some cases, the ions may be nitrogen ions and a lithium nitride layer may be formed on the lithium metal surface. In other embodiments, the protective layer may be formed by converting lithium to lithium nitride at high pressures. Other methods for forming protective layers are also provided.

  5. Solid state NMR and pair distribution function studies of silicon electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Key, Baris

    The universally used negative electrode material in a LIB is carbon, because of its moderate capacity (372 mAhg-1 for graphite), cyclability and high rate capability. However, new, low cost, safe electrode materials with higher capacities are still urgently required for both portable and transportation applications. Silicon anodes are particularly attractive alternatives to carbon with extremely high gravimetric energy densities (3572 mAhg-1). Compared to graphite, silicon has a massive volumetric capacity of 8322 mAhcm-3 (calculated based on the original volume of silicon) which is approximately ten times that graphite. At room temperature, upon electrochemical lithiation, silicon undergoes a crystalline to amorphous phase transition forming a lithiated amorphous silicide phase. Unfortunately, due to the amorphous nature of the lithiated silicides, it is not possible to monitor all the structural changes that occur during lithium insertion/removal with conventional methods such as diffraction. The short range order of the amorphous materials remains unknown, preventing attempts to optimize performance based on electrochemical-structure correlations. In this work, a combination of local structure probes, ex-situ 7Li nuclear magnetic resonance (NMR) studies and pair distribution function (PDF) analysis of X-ray data was applied to investigate the changes in short range order that occur during the initial charge and discharge cycles. The distinct electrochemical profiles observed subsequent to the 1 st discharge have been shown to be associated with the formation of distinct amorphous lithiated silicide structures. A (de)lithiation model consisting of four different mechanisms, each being valid for regions of the charge or discharge process is proposed to explain the hysteresis and the steps in the electrochemical profile observed during lithiation and delithiation of Si. A spontaneous reaction of the fully lithiated lithium silicide with the electrolyte is directly

  6. Mo/sub 6/Se/sub 6/: A new solid-state electrode for secondary lithium batteries

    SciTech Connect

    Tarascon, J.M.

    1985-09-01

    The practical utilization of nonaqueous secondary lithium cells has never been realized, mainly because of electrode problems such as the absence of suitable cathode materials or dendritic regrowth of the lithium on the anode short circuiting the cell. Over the last few years, the cathode problem has been overcome by the discovery of new materials such as TiS/sub 2/, NbSe/sub 3/, V/sub 6/O/sub 13/, etc. The crystallographic structural feature that makes these compounds attractive for batteries is that they can act as ''hosts,'' incorporating lithium atoms between the layers (TiS/sub 2/), chains (NbSe/sub 3/), or into the channels (V/sub 6/O/sub 13/) without a irreversible change in crystal structure. However, in spite of intensive research, the anode problem still remains. We have undertaken research in this direction. Initial results of this early work are the subject of this paper. This study reports a new solid-state electrode material (Mo/sub 6/Se/sub 6/) which can be used both as cathode and anode in secondary lithium cells. Mo/sub 6/Se/sub 6/ can take up reversibly nine lithium atoms per Mo/sub 6/Se/sub 6/ without losing its linear chain structure, leading to a theoretical volume energy density of about 1.1 Wh/cm/sup 3/, compared to 1.2 for TiS/sub 2/ cathodes. Another important promising possibility which arises from this work is the use of the lithiated compounds LiMo/sub 6/Se/sub 6/ as the anode instead of lithium metal in secondary lithium cells.

  7. Impacts of Surface Energy on Lithium Ion Intercalation Properties of V2O5.

    PubMed

    Ma, Wenda; Zhang, Changkun; Liu, Chaofeng; Nan, Xihui; Fu, Haoyu; Cao, Guozhong

    2016-08-01

    Oxygen vacancies have demonstrated to be one of the most effective ways to alter electrochemical performance of electrodes for lithium ion batteries, though there is little information how oxygen vacancies affect the electrochemical properties. Vanadium pentoxide (V2O5) cathode has been investigated to explore the relationship among oxygen vacancies, surface energy, and electrochemical properties. The hydrogen-treated V2O5 (H-V2O5) sample synthesized via thermal treatment under H2 atmosphere possesses a high surface energy (63 mJ m(-2)) as compared to that of pristine V2O5 (40 mJ m(-2)) and delivers a high reversible capacity of 273.4 mAh g(-1) at a current density of 50 mA g(-1), retaining 189.0 mAh g(-1) when the current density increases to 2 A g(-1). It also displays a capacity retention of 92% after 100 cycles at 150 mA g(-1). The presence of surface oxygen vacancies increases surface energy and possibly serves as a nucleation center to facilitate phase transition during lithium ion intercalation and deintercalation processes. PMID:27400230

  8. Physics of electron and lithium-ion transport in electrode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Musheng, Wu; Bo, Xu; Chuying, Ouyang

    2016-01-01

    The physics of ionic and electrical conduction at electrode materials of lithium-ion batteries (LIBs) are briefly summarized here, besides, we review the current research on ionic and electrical conduction in electrode material incorporating experimental and simulation studies. Commercial LIBs have been widely used in portable electronic devices and are now developed for large-scale applications in hybrid electric vehicles (HEV) and stationary distributed power stations. However, due to the physical limits of the materials, the overall performance of today’s LIBs does not meet all the requirements for future applications, and the transport problem has been one of the main barriers to further improvement. The electron and Li-ion transport behaviors are important in determining the rate capacity of LIBs. Project supported by the National High Technology Research and Development Program of 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 and 20142BAB212002), and the Foundation of Jiangxi Education Committee, China (Grant Nos. GJJ14254 and KJLD14024). C. Y. Ouyang is also supported by the “Gan-po talent 555” Project of Jiangxi Province, China.

  9. Layered manganese oxide intergrowth electrodes for rechargeable lithium batteries: Part 2. Substitution with Al

    SciTech Connect

    Patoux, Sebastien; Dolle, Mickael; Doeff, Marca M.

    2004-09-08

    The structural and electrochemical characterization of layered Li{sub x}Al{sub y}Mn{sub 1-y}O{sub 2} compounds prepared from sodium-containing precursors is described. A quaternary phase diagram showing composition ranges for pure P2 and P3 structures and P2/P3 intergrowths obtained in the Na-Al-Mn-O system is presented. Upon ion exchange, these compounds change to O2, O3 or O2/O3 stacking arrangements, respectively. The oxygen array in O3 and spinel structures is similar, and most of the O3 structures convert to spinel rapidly upon electrochemical cycling in lithium cells. This process is delayed somewhat by increased Al substitution, but not completely inhibited. More effective suppression of the phase transformation is observed in O2/O3 intergrowth electrodes. Additionally, the capacity retention upon cycling and the rate behavior of cells containing intergrowth electrodes is superior to those with pure O2 structures.

  10. The transformation of graphite electrode materials in lithium-ion batteries after cycling

    NASA Astrophysics Data System (ADS)

    Dai, Kehua; Wang, Zhihui; Ai, Guo; Zhao, Hui; Yuan, Wen; Song, Xiangyun; Battaglia, Vincent; Sun, Chengdong; Wu, Kai; Liu, Gao

    2015-12-01

    To reveal how graphite electrodes change with cycling in lithium-ion batteries, electrochemical experiments involving charge-discharge cycling at different current density conditions are performed on commercial pouch cells and the graphite electrodes after cycling. This research shows that the polyvinylidene fluoride (PVDF) binder does not degrade, confirmed by the stable molecular weight after different cycling conditions. Particle size analysis results indicate that the diameter of graphite particles after cycling is ∼10% larger than that of the graphite before cycling, which results in a ∼30% volume expansion after cycling. For the cells cycled at the same current density, the graphite particle size increases with cycle time. For the cells with the same cycle numbers, the graphite particle size is larger in the cells cycled at lower current density. X-ray diffraction characterization shows that the d-spacings of the graphite particles in all the cells at different cycling conditions are identical. These results suggest that the graphite particle size increase associated with cycling may arise specifically when primary particles inflate the secondary particle size, leading to dramatic volume expansion of graphite secondary particles.

  11. Conducting polymer-skinned electroactive materials of lithium-ion batteries: ready for monocomponent electrodes without additional binders and conductive agents.

    PubMed

    Kim, Ju-Myung; Park, Han-Saem; Park, Jang-Hoon; Kim, Tae-Hee; Song, Hyun-Kon; Lee, Sang-Young

    2014-08-13

    Rapid growth of mobile and even wearable electronics is in pursuit of high-energy-density lithium-ion batteries. One simple and facile way to achieve this goal is the elimination of nonelectroactive components of electrodes such as binders and conductive agents. Here, we present a new concept of monocomponent electrodes comprising solely electroactive materials that are wrapped with an insignificant amount (less than 0.4 wt %) of conducting polymer (PEDOT:PSS or poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate)). The PEDOT:PSS as an ultraskinny surface layer on electroactive materials (LiCoO2 (LCO) powders are chosen as a model system to explore feasibility of this new concept) successfully acts as a kind of binder as well as mixed (both electrically and ionically) conductive film, playing a key role in enabling the monocomponent electrode. The electric conductivity of the monocomponent LCO cathode is controlled by simply varying the PSS content and also the structural conformation (benzoid-favoring coil structure and quinoid-favoring linear or extended coil structure) of PEDOT in the PEDOT:PSS skin. Notably, a substantial increase in the mass-loading density of the LCO cathode is realized with the PEDOT:PSS skin without sacrificing electronic/ionic transport pathways. We envisage that the PEDOT:PSS-skinned electrode strategy opens a scalable and versatile route for making practically meaningful binder-/conductive agent-free (monocomponent) electrodes. PMID:24988178

  12. High surface area electrode for high efficient microbial electrosynthesis

    NASA Astrophysics Data System (ADS)

    Nie, Huarong; Cui, Mengmeng; Lu, Haiyun; Zhang, Tian; Russell, Thomas; Lovley, Derek

    2012-02-01

    Microbial electrosynthesis, a process in which microorganisms directly accept electrons from an electrode to convert carbon dioxide and water into multi carbon organic compounds, affords a novel route for the generation of valuable products from electricity or even wastewater. The surface area of the electrode is critical for high production. A biocompatible, highly conductive, three-dimensional cathode was fabricated from a carbon nanotube textile composite to support the microorganism to produce acetate from carbon dioxide. The high surface area and macroscale porous structure of the intertwined CNT coated textile ?bers provides easy microbe access. The production of acetate using this cathode is 5 fold larger than that using a planar graphite electrode with the same volume. Nickel-nanowire-modified carbon electrodes, fabricated by microwave welding, increased the surface area greatly, were able to absorb more bacteria and showed a 1.5 fold increase in performance

  13. Synthesis and effect of electrode heat-treatment on the superior lithium storage performance of Co3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhang, Jingjing; Huang, Tao; Yu, Aishui

    2015-01-01

    Single-crystal Co3O4 nanoparticles are produced via a novel lysine-assisted hydrothermal process. When used as anode materials for lithium-ion batteries, a heat-treatment process is first introduced to decrease the initial irreversible loss and enhance the cyclability of Co3O4 nanoparticle-based electrodes using a polyvinylidene fluoride (PVDF) binder. Heat-treated electrodes exhibit improved lithium storage properties relative to those that are unheated. In particular, Co3O4 electrodes heated at 200 °C have the highest capacity and best reversibility: 1000 mA h g-1 with 95.2% capacity retention after 170 cycles at a current density of 100 mA g-1. Even when cycled at a high rate of 1000 mA g-1, a reversible capacity up to 600 mA h g-1 can still be maintained after 500 cycles. These improvements are explained based on the results from thermal analysis, transmission electron microscopy, scanning electron microscopy, nanoscratch tests, and electrochemical impedance spectroscopy measurements. Heat treatment not only improves binder distribution and adhesion to both Co3O4 particles and the substrate but also ensures high interfacial conductivity and keeps the active material particles and carbon black electrically connected, thereby leading to superior electrochemical performance. The results suggest that the heat-treated Co3O4 electrode may be a promising anode for next-generation lithium-ion batteries.

  14. A Convenient and Versatile Method To Control the Electrode Microstructure toward High-Energy Lithium-Ion Batteries.

    PubMed

    Zhao, Hui; Yang, Qing; Yuca, Neslihan; Ling, Min; Higa, Kenneth; Battaglia, Vincent S; Parkinson, Dilworth Y; Srinivasan, Venkat; Liu, Gao

    2016-07-13

    Control over porous electrode microstructure is critical for the continued improvement of electrochemical performance of lithium ion batteries. This paper describes a convenient and economical method for controlling electrode porosity, thereby enhancing material loading and stabilizing the cycling performance. Sacrificial NaCl is added to a Si-based electrode, which demonstrates an areal capacity of ∼4 mAh/cm(2) at a C/10 rate (0.51 mA/cm(2)) and an areal capacity of 3 mAh/cm(2) at a C/3 rate (1.7 mA/cm(2)), one of the highest material loadings reported for a Si-based anode at such a high cycling rate. X-ray microtomography confirmed the improved porous architecture of the SiO electrode with NaCl. The method developed here is expected to be compatible with the state-of-the-art lithium ion battery industrial fabrication processes and therefore holds great promise as a practical technique for boosting the electrochemical performance of lithium ion batteries without changing material systems. PMID:27336856

  15. Effect of back-side-coated electrodes on electrochemical performances of lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Yunju; Son, Bongki; Choi, Jaecheol; Kim, Jong Hun; Ryou, Myung-Hyun; Lee, Yong Min

    2015-02-01

    In order to investigate the effect of back-side coating of cathodes and anodes upon electrochemical performances of lithium-ion batteries (LIBs), four different pouch-type lithium cobalt oxide (LiCoO2, LCO)/graphite unit cells with different coating conditions are prepared and compared in a systematic manner. Their electrochemical performance, in terms of Coulombic efficiency, capacity realization, capacity retention ability, and rate capabilities, is investigated. From the results, we confirm an opposing relationship existing between back-side-coated cathodes and anodes, in that the coated cathodes provide improved cell performance, while the coated anodes impede it. This is attributed to the fact that, as is generally understood, cathodes act as noble lithium (Li) ion suppliers for LIBs, while anodes consume a large portion of Li ions to form surface layers during the first charging process. Furthermore, we also confirm that the magnitude of the back-side coating effect for LCO and graphite are somewhat different. The double-side-coated cathodes have a notable positive effect on cell performances in contrast to the negative effect seen with the double-side-coated anodes. As a result, unit cells employing double-side-coated cathodes with single-side-coated anodes show the best performance, followed by those based on double-side-coated cathodes with double-side-coated anodes rather than single-side-coated cathodes with single-side coated anodes.

  16. Chemical State of Surface Oxygen on Carbon and Its Effects on the Capacity of the Carbon Anode in a Lithium-Ion Battery Investigated

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    2001-01-01

    In a lithium-ion battery, the lithium-storage capacity of the carbon anode is greatly affected by a surface layer formed during the first half cycle of lithium insertion and release into and out of the carbon anode. The formation of this solid-electrolyte interface, in turn, is affected by the chemistry of the carbon surface. A study at the NASA Glenn Research Center examined the cause-and-effect relations. Information obtained from this research could contribute in designing a high-capacity lithium-ion battery and, therefore, small, powerful spacecraft. In one test, three types of surfaces were examined: (1) a surface with low oxygen content (1.5 at.%) and a high concentration of active sites, (2) a surface with 4.5 at.% -OH or -OC type oxygen, and (3) a surface with 6.5 at.% O=C type oxygen. The samples were made from the same precursor and had similar bulk properties. They were tested under a constant current of 10 mA/g in half cells that used lithium metal as the counter electrode and 0.5 M lithium iodide in 50/50 (vol%) ethylene carbonate and dimethyl carbonate as the electrolyte. For the first cycle of the electrochemical test, the graph describes the voltage of the carbon anode versus the lithium metal as a function of the capacity (amount of lithium insertion or release). From these data, it can be observed that the surface with low oxygen and a high concentration of active sites could result in a high irreversible capacity. Such a high irreversible capacity could be prevented if the active sites were allowed to react with oxygen in air, producing -OH or -OC type oxygen. The O=C type oxygen, on the other hand, could greatly reduce the capacity of lithium intercalation and, therefore, needs to be avoided during battery fabrication.

  17. Surface studies of lithium-oxygen redox reactions over HOPG

    NASA Astrophysics Data System (ADS)

    Marchini, Florencia; Herrera, Santiago E.; Calvo, Ernesto J.; Williams, Federico J.

    2016-04-01

    The O2/Li2O2 electrode reaction has been studied on low surface area HOPG electrodes in 0.1 M LiPF6 in dimethyl sulfoxide (DMSO) electrolyte. Studies were performed using electrochemical cells coupled to a XPS spectrometer and to an AFM microscope. AFM images after electrochemical treatment at cathodic potentials exhibited 20 to 100 nm in height features, whereas anodic treatment showed a thin film of about 1 nm thickness deposited over the HOPG electrode. XPS spectra after electrochemical treatment showed surface species due to DMSO and LiPF6 decomposition. These findings indicate the high reactivity of oxygen reduction products towards the electrolyte and the solvent. The unwanted deposits formed under electrochemical operation cannot be completely eliminated from the surface even after applying high anodic potentials. This highlights the known loss of capacity of Li-air batteries, issue that must be overcome for successful applications.

  18. Composition analysis of the passive film on the carbon electrode of a lithium-ion battery with an EC-based electrolyte

    NASA Astrophysics Data System (ADS)

    Yang, C. R.; Wang, Y. Y.; Wan, C. C.

    This work examines the formation of a passive film on the carbon electrode of lithium-ion batteries. With a single solvent of EC (ethylene carbonate), the structure of the passive film is found to be (CH 2OCOOLi) 2. In a DEC (diethyl carbonate) or DMC (dimethyl carbonate) system, C 2H 5OCOOLi and Li 2CO 3 are formed on the surface of the carbon electrode. According to results from mass spectra, CO 2 gas is the main product when EC is decomposed. By contrast, DEC is decomposed into CO and C 2H 6, and DMC into CO and CH 4. These findings suggest that the composition of the passive film depends on the chosen solvent. In a binary solvent system which contains EC, the passive film contains chiefly (CH 2OCOOLi) 2, which is identical to a single EC solvent system.

  19. Lithium

    USGS Publications Warehouse

    Ober, J.

    1998-01-01

    The lithium industry can be divided into two sectors: ore concentrate producers and chemical producers. Ore concentrate producers mine lithium minerals. They beneficiate the ores to produce material for use in ceramics and glass manufacturing.

  20. Virus enabled 3d nano-array electrodes for integrated Lithium/Sodium-ion microbatteries

    NASA Astrophysics Data System (ADS)

    Liu, Yihang

    Multilayers of functional materials (carbon/electrode/nickel) were hierarchically architectured over tobacco mosaic virus (TMV) templates that were genetically modified to self-assemble in a vertical manner on current-collectors for battery applications. The spaces formed between individual rods effectively accommodated the volume expansion and contraction of electrodes during charge/discharge, while surface carbon coating engineered over these nanorods further enhance the electronic conductivity. The microbattery based on self aligned nanoforests with precise arrangement of various auxiliary material layers including a central nanometric metal core as direct electronic pathway to current collector, can deliver high energy density and stable cycling stability. C/LiFePO4/Ni/TMV nanoforest cathodes for Li-ion batteries and C/Sn/Ni/TMV nanoforest anodes for Na-ion batteries were assembled using physical sputtering deposition. Both 3D nanoforest electrodes show exceptional cycling stability and rate capability.

  1. Diaphragmatic activity induced by cortical stimulation: surface versus esophageal electrodes.

    PubMed

    Gea, J; Espadaler, J M; Guiu, R; Aran, X; Seoane, L; Broquetas, J M

    1993-02-01

    Evoked responses of the diaphragm can be induced by magnetic cortical stimulation and recorded by either surface or esophageal electrodes. The former recording system is tolerated better by the patient but has potential problems with the specificity of the diaphragmatic signal. This study compares the responses of the diaphragm to cortical stimulation that were recorded simultaneously with surface and esophageal electrodes on seven patients (61 +/- 4 yr) with chronic obstructive pulmonary diseases. Stimuli were delivered in three ventilatory conditions: at baseline, during deep breathing, and during voluntary panting. No differences were observed between results recorded by surface and esophageal electrodes [amplitude of the compound motor of the action potential (CMAP), 0.8 +/- 0.1 vs. 0.8 +/- 0.1 mV, NS; latency, 13.1 +/- 0.4 vs. 12.6 +/- 0.5 ms, NS]. In addition, significant correlations were found (CMAP, r = 0.77, P < 0.001; latency, r = 0.71, P = 0.002). The concordance analysis, however, indicated some dissimilarity between the recordings of the electrodes (CMAP, R1 = 0.31; latency, R1 = 0.26). These differences may be due to the area of the muscle mainly recorded by each electrode and/or to the additional activity from other muscles recorded by surface electrodes. On the other hand, the diaphragmatic responses observed in these patients with chronic obstructive pulmonary diseases were similar to those previously reported in healthy subjects. PMID:8458780

  2. Lithium intercalation behavior of surface modified carbonaceous materials

    SciTech Connect

    Tran, T.D.; Murguia, L.X.; Song, X.; Kinoshita, K.

    1997-07-17

    The surface properties of several well-characterized commercial carbon materials were modified by thermal and chemical treatments. The reversible capacities for lithium intercalation of a sponge green coke and a fuel green coke for lithium intercalation increased by as much as 25% after heat treatment in both reducing (5% H{sub 2}/Ar) and oxidizing (CO{sub 2}) environments. The irreversible capacity loss increased significantly with CO{sub 2} treatment at 800{degrees}C. The trend of larger capacity losses with CO{sub 2} treatment is also observed with a synthetic graphite (SFG6) which was produced by heat treatment at about 3000{degrees}C. Carbon fibers that were first impregnated with LiOH solution followed by reaction with CO{sub 2} to form Li{sub 2}CO{sub 3} tended to show lower irreversible capacity losses.

  3. Stability of carbon electrodes for aqueous lithium-air secondary batteries

    NASA Astrophysics Data System (ADS)

    Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

    2014-01-01

    The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

  4. Spreading of lithium on a stainless steel surface at room temperature

    NASA Astrophysics Data System (ADS)

    Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

    2016-01-01

    Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. The spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (Edes = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (Edes = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium-lithium bonding.

  5. Spreading of lithium on a stainless steel surface at room temperature

    SciTech Connect

    Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

    2015-11-10

    Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (Edes = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (Edes = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.

  6. Spreading of lithium on a stainless steel surface at room temperature

    DOE PAGESBeta

    Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

    2015-11-10

    Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separatemore » experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (Edes = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (Edes = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.« less

  7. Spreading of lithium on a stainless steel surface at room temperature

    SciTech Connect

    Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

    2016-01-01

    Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. The spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 mu m/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (E-des = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (E-des = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding. (C) 2015 Elsevier B.V. All rights reserved.

  8. Advanced Mesoporous Spinel Li4Ti5O12/rGO Composites with Increased Surface Lithium Storage Capability for High-Power Lithium-Ion Batteries.

    PubMed

    Ge, Hao; Hao, Tingting; Osgood, Hannah; Zhang, Bing; Chen, Li; Cui, Luxia; Song, Xi-Ming; Ogoke, Ogechi; Wu, Gang

    2016-04-13

    Spinel Li4Ti5O12 (LTO) and reduced graphene oxide (rGO) are attractive anode materials for lithium-ion batteries (LIBs) because of their unique electrochemical properties. Herein, we report a facile one-step hydrothermal method in preparation of a nanocomposite anode consisting of well-dispersed mesoporous LTO particles onto rGO. An important reaction step involves glucose as a novel linker agent and reducing agent during the synthesis. It was found to prevent the aggregation of LTO particles, and to yield mesoporous structures in nanocomposites. Moreover, GO is reduced to rGO by the hydroxyl groups on glucose during the hydrothermal process. When compared to previously reported LTO/graphene electrodes, the newly prepared LTO/rGO nanocomposite has mesoporous characteristics and provides additional surface lithium storage capability, superior to traditional LTO-based materials for LIBs. These unique properties lead to markedly improved electrochemical performance. In particular, the nanocomposite anode delivers an ultrahigh reversible capacity of 193 mA h g(-1) at 0.5 C and superior rate performance capable of retaining a capacity of 168 mA h g(-1) at 30 C between 1.0 and 2.5 V. Therefore, the newly prepared mesoporous LTO/rGO nanocomposite with increased surface lithium storage capability will provide a new opportunity to develop high-power anode materials for LIBs. PMID:27015357

  9. Li-ion capacitors with carbon cathode and hard carbon/stabilized lithium metal powder anode electrodes

    NASA Astrophysics Data System (ADS)

    Cao, W. J.; Zheng, J. P.

    2012-09-01

    A lithium-ion capacitor was developed using a mixture of stabilized lithium metal powder and hard carbon as the anode electrode, while activated carbon was used as the cathode. A specific energy of approximately 82 Wh kg-1 was obtained based on the weight of electrode materials; however, when the electrolyte, separator, and current collectors were included, the specific energy of an assembled Li-ion capacitor was about 25 Wh kg-1. The capacitor was able to deliver over 60% of the maximum energy at a discharge C-rate of 44C. Through continuous galvanostatic charge/discharge cycling, the capacitance of the Li-ion capacitor degraded less than 3% over 600 cycles.

  10. Facile fabrication of binder-free NiO electrodes with high rate capacity for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gu, Lili; Xie, Wenhe; Bai, Shuai; Liu, Boli; Xue, Song; Li, Qun; He, Deyan

    2016-04-01

    NiO nanocone arrays are fabricated on nickel foam substrate by a simple hydrothermal synthesis and a subsequent annealing in air. The obtained architecture is directly used as an anode for lithium-ion batteries without any binder. It delivers a capacity of 969 mAh g-1 in the 120th cycle at a current density of 0.5 C. Even at 10 C, the electrode can still deliver a capacity as high as 605.9 mAh g-1. The excellent electrochemical performance could be ascribed to the integrity and porosity of the cycled electrodes.

  11. Quantifying Bulk Electrode Strain and Material Displacement within Lithium Batteries via High‐Speed Operando Tomography and Digital Volume Correlation

    PubMed Central

    Finegan, Donal P.; Tudisco, Erika; Scheel, Mario; Robinson, James B.; Taiwo, Oluwadamilola O.; Eastwood, David S.; Lee, Peter D.; Di Michiel, Marco; Bay, Brian; Hall, Stephen A.; Hinds, Gareth; Brett, Dan J. L.

    2015-01-01

    Tracking the dynamic morphology of active materials during operation of lithium batteries is essential for identifying causes of performance loss. Digital volume correlation (DVC) is applied to high‐speed operando synchrotron X‐ray computed tomography of a commercial Li/MnO2 primary battery during discharge. Real‐time electrode material displacement is captured in 3D allowing degradation mechanisms such as delamination of the electrode from the current collector and electrode crack formation to be identified. Continuum DVC of consecutive images during discharge is used to quantify local displacements and strains in 3D throughout discharge, facilitating tracking of the progression of swelling due to lithiation within the electrode material in a commercial, spiral‐wound battery during normal operation. Displacement of the rigid current collector and cell materials contribute to severe electrode detachment and crack formation during discharge, which is monitored by a separate DVC approach. Use of time‐lapse X‐ray computed tomography coupled with DVC is thus demonstrated as an effective diagnostic technique to identify causes of performance loss within commercial lithium batteries; this novel approach is expected to guide the development of more effective commercial cell designs. PMID:27610334

  12. Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

    NASA Astrophysics Data System (ADS)

    Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

    2016-03-01

    Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

  13. Polypyrrole-encapsulated vanadium pentoxide nanowires on a conductive substrate for electrode in aqueous rechargeable lithium battery.

    PubMed

    Liang, Chaowei; Fang, Dong; Cao, Yunhe; Li, Guangzhong; Luo, Zhiping; Zhou, Qunhua; Xiong, Chuanxi; Xu, Weilin

    2015-02-01

    Precursors of ammonium vanadium bronze (NH4V4O10) nanowires assembled on a conductive substrate were prepared by a hydrothermal method. After calcination at 360°C, the NH4V4O10 precursor transformed to vanadium pentoxide (V2O5) nanowires, which presented a high initial capacity of 135.0mA h g(-1) at a current density of 50mA g(-1) in 5M LiNO3 aqueous solution; while the specific capacity faded quickly over 50 cycles. By coating the surface of V2O5 nanowires with water-insoluble polypyrrole (PPy), the formed nanocomposite electrode exhibited a specific discharge capacity of 89.9mA h g(-1) at 50mA g(-1) (after 100 cycles). A V2O5@PPy //LiMn2O4 rechargeable lithium battery exhibited an initial discharge capacity of 95.2mA h g(-1); and after 100 cycles, a specific discharge capacity of 81.5mA h g(-1) could retain at 100mA g(-1). PMID:25463177

  14. A Long-Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution.

    PubMed

    Elia, Giuseppe Antonio; Ulissi, Ulderico; Mueller, Franziska; Reiter, Jakub; Tsiouvaras, Nikolaos; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

    2016-05-10

    In this paper, we report an advanced long-life lithium ion battery, employing a Pyr14 TFSI-LiTFSI non-flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn-C) nanocomposite anode, and a layered LiNi1/3 Co1/3 Mn1/3 O2 (NMC) cathode. The IL-based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel-Tammann-Fulcher (VTF) trend. Lithium half-cells employing the Sn-C anode and NMC cathode in the Pyr14 TFSI-LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn-C electrodes are combined into a cathode-limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g(-1) and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL-based lithium ion cells are suitable batteries for application in electric vehicles. PMID:26990320

  15. Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam

    PubMed Central

    Lin, Feng; Markus, Isaac M.; Doeff, Marca M.; Xin, Huolin L.

    2014-01-01

    The investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. However, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi0.4Mn0.4Co0.18Ti0.02O2 particles, repeated electron beam irradiation induced a phase transition from an layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results. PMID:25027190

  16. Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam

    NASA Astrophysics Data System (ADS)

    Lin, Feng; Markus, Isaac M.; Doeff, Marca M.; Xin, Huolin L.

    2014-07-01

    The investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. However, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi0.4Mn0.4Co0.18Ti0.02O2 particles, repeated electron beam irradiation induced a phase transition from an layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results.

  17. Chemical and structural stability of lithium-ion battery electrode materials under electron beam.

    PubMed

    Lin, Feng; Markus, Isaac M; Doeff, Marca M; Xin, Huolin L

    2014-01-01

    The investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. However, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi(0.4)Mn(0.4)Co(0.18)Ti(0.02)O2 particles, repeated electron beam irradiation induced a phase transition from an layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results. PMID:25027190

  18. Understanding capacity fade in silicon based electrodes for lithium-ion batteries using three electrode cells and upper cut-off voltage studies

    NASA Astrophysics Data System (ADS)

    Beattie, Shane D.; Loveridge, M. J.; Lain, Michael J.; Ferrari, Stefania; Polzin, Bryant J.; Bhagat, Rohit; Dashwood, Richard

    2016-01-01

    Commercial Li-ion batteries are typically cycled between 3.0 and 4.2 V. These voltages limits are chosen based on the characteristics of the cathode (e.g. lithium cobalt oxide) and anode (e.g. graphite). When alternative anode/cathode chemistries are studied the same cut-off voltages are often, mistakenly, used. Silicon (Si) based anodes are widely studied as a high capacity alternative to graphite for Lithium-ion batteries. When silicon-based anodes are paired with high capacity cathodes (e.g. Lithium Nickel Cobalt Aluminium Oxide; NCA) the cell typically suffers from rapid capacity fade. The purpose of this communication is to understand how the choice of upper cut-off voltage affects cell performance in Si/NCA cells. A careful study of three-electrode cell data will show that capacity fade in Si/NCA cells is due to an ever-evolving silicon voltage profile that pushes the upper voltage at the cathode to >4.4 V (vs. Li/Li+). This behaviour initially improves cycle efficiency, due to liberation of new lithium, but ultimately reduces cycling efficiency, resulting in rapid capacity fade.

  19. Transitions from near-surface to interior redox upon lithiation in conversion electrode materials

    SciTech Connect

    He, Kai; Xin, Huolin L.; Zhao, Kejie; Yu, Xiqian; Norlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A.; Richards, Ryan M.; Doeff, Marca M.; Yang, Xiao-Qing; Stach, Eric A.; Li, Ju; Lin, Feng; Su, Dong

    2015-01-29

    Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni²⁺→Ni⁰) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a “shrinking-core” mode). However, the interior capacity for Ni²⁺→Ni⁰ can be accessed efficiently following the nucleation of lithiation “fingers” which propagate into the sample bulk, but only after a certain incubation time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries, and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss, and provides guidance for the further design of battery materials that favors high C-rate charging.

  20. Transitions from near-surface to interior redox upon lithiation in conversion electrode materials

    DOE PAGESBeta

    He, Kai; Xin, Huolin L.; Zhao, Kejie; Yu, Xiqian; Norlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A.; Richards, Ryan M.; et al

    2015-01-29

    Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni²⁺→Ni⁰) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a “shrinking-core” mode). However, the interior capacity for Ni²⁺→Ni⁰ can be accessed efficiently following the nucleation of lithiation “fingers” which propagate into the sample bulk, but only after a certain incubationmore » time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries, and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss, and provides guidance for the further design of battery materials that favors high C-rate charging.« less

  1. Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design.

    PubMed

    An, Yonghao; Wood, Brandon C; Ye, Jianchao; Chiang, Yet-Ming; Wang, Y Morris; Tang, Ming; Jiang, Hanqing

    2015-07-21

    Although crystalline silicon (c-Si) anodes promise very high energy densities in Li-ion batteries, their practical use is complicated by amorphization, large volume expansion and severe plastic deformation upon lithium insertion. Recent experiments have revealed the existence of a sharp interface between crystalline Si (c-Si) and the amorphous LixSi alloy during lithiation, which propagates with a velocity that is orientation dependent; the resulting anisotropic swelling generates substantial strain concentrations that initiate cracks even in nanostructured Si. Here we describe a novel strategy to mitigate lithiation-induced fracture by using pristine c-Si structures with engineered anisometric morphologies that are deliberately designed to counteract the anisotropy in the crystalline/amorphous interface velocity. This produces a much more uniform volume expansion, significantly reducing strain concentration. Based on a new, validated methodology that improves previous models of anisotropic swelling of c-Si, we propose optimal morphological designs for c-Si pillars and particles. The advantages of the new morphologies are clearly demonstrated by mesoscale simulations and verified by experiments on engineered c-Si micropillars. The results of this study illustrate that morphological design is effective in improving the fracture resistance of micron-sized Si electrodes, which will facilitate their practical application in next-generation Li-ion batteries. The model and design approach present in this paper also have general implications for the study and mitigation of mechanical failure of electrode materials that undergo large anisotropic volume change upon ion insertion and extraction. PMID:26082019

  2. Morphology-Tuned Synthesis of NiCo2 O4 -Coated 3D Graphene Architectures Used as Binder-Free Electrodes for Lithium-Ion Batteries.

    PubMed

    Zhang, Chunfei; Yu, Jong-Sung

    2016-03-18

    Nanostructured NiCo2 O4 is directly grown on the surface of three-dimensional graphene-coated nickel foam (3D-GNF) by a facile electrodeposition technique and subsequent annealing. The resulting NiCo2 O4 possesses a distinct flower or sheet morphology, tuned by potential or current variation electrodeposition, which are used as binder-free lithium-ion battery anodes for the first time. Both samples exhibit high lithium storage capacity, profiting from the unique binder-free electrode structures. The flower-type NiCo2 O4 demonstrates high reversible discharge capacity (1459 mAh g(-1) at 200 mA g(-1) ) and excellent cyclability with around 71 % retention of the reversible capacity after 60 cycles, which are superior to the sheet-type NiCo2 O4 . Such superb performance can be attributed to high volume utilization efficiency with unique morphological character, a well-preserved connection between the active materials and the current collector, a short lithium-ion diffusion path, and fast electrolyte transfer in the binder-free NiCo2 O4 -coated 3D graphene structure. The simple preparation process and easily controllable morphology make the binder-free NiCo2 O4 /3D-GNF hybrid a potential material for commercial applications. PMID:26918287

  3. Holographic surface gratings in iron-doped lithium niobate

    SciTech Connect

    Sarkisov, S. S.; Curley, M. J.; Kukhtarev, N. V.; Fields, A.; Adamovsky, G.; Smith, C. C.; Moore, L. E.

    2001-08-13

    Surface gratings associated with holographic volume gratings in photorefractive crystals of iron-doped lithium niobate have been studied using diffraction of a reflected probe beam and high-resolution phase-shifted interferometric profilometry. Both techniques show that the surface gratings exist in the form of periodical corrugations of the same period as that of the volume grating. The maximum amplitude of the periodical surface relief measured by both techniques is close to 6.5 nm. We also demonstrated that the periodical electric forces on the surface were capable of assembling polystyrene microspheres along the fringes of the grating. Large amplitude of the periodic electric field (1.6 x 10{sup 4}V/cm) is associated with the photogalvanic effect. {copyright} 2001 American Institute of Physics.

  4. Field-free junctions for surface electrode ion traps

    NASA Astrophysics Data System (ADS)

    Jordens, Robert; Schmied, R.; Blain, M. G.; Leibfried, D.; Wineland, D.

    2015-05-01

    Intersections between transport guides in a network of RF ion traps are a key ingredient to many implementations of scalable quantum information processing with trapped ions. Several junction architectures demonstrated so far are limited by varying radial secular frequencies, a reduced trap depth, or a non-vanishing RF field along the transport channel. We report on the design and progress in implementing a configurable microfabricated surface electrode Y-junction that employs switchable RF electrodes. An essentially RF-field-free pseudopotential guide between any two legs of the junction can be established by applying RF potential to a suitable pair of electrodes. The transport channel's height above the electrodes, its depth and radial curvature are constant to within 15%. Supported by IARPA, Sandia, NSA, ONR, and the NIST Quantum Information Program.

  5. Incorporation of conductive polymer into soft carbon electrodes for lithium ion capacitors

    NASA Astrophysics Data System (ADS)

    Lim, Young-Geun; Park, Min-Sik; Kim, Ki Jae; Jung, Kyu-Sung; Kim, Jung Ho; Shahabuddin, Mohammed; Byun, Dongjin; Yu, Ji-Sang

    2015-12-01

    The positive effects of incorporating electrically conductive poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS) into the negative electrode (NE) of a lithium ion capacitor (LIC) is investigated. The binding material of the NE, styrene-butadiene rubber (SBR), is partially substituted by conductive PEDOT-PSS. The soft carbon NE with 1.0 wt% PEDOT-PSS exhibits enhanced capacity retention of 64% at a current density of 5 C by lowering its electrical and electrochemical charge transfer resistance. The rate capability increased with increasing amounts of PEDOT-PSS, with no variation in the Li+ diffusivity. This improved electrochemical performance of the NE is also reflected in the LIC full-cell configuration. An LIC employing a 1.0 wt% PEDOT-PSS NE delivers 6.6 F at a high current density of 100 C, which is higher than the 6.0 F measured for the LIC with a bare NE. Moreover, the LIC with the 1.0 wt% PEDOT-PSS NE retains 85% of its initial capacitance even after 5000 cycles. These results are mainly attributed to the favourable electrical network formed by the incorporation of PEDOT-PSS into the NE. Thus, we believe that the incorporation of conductive PEDOT-PSS is a viable approach for obtaining high-power LICs.

  6. Molecular-Confinement of Polysulfide within Mesoscale Electrodes for the Practical Application of Lithium Sulfur Batteries

    SciTech Connect

    Chen, Junzheng; Wu, Dangxin; Walter, Eric D.; Engelhard, Mark H.; Bhattacharya, Priyanka; Pan, Huilin; Shao, Yuyan; Gao, Fei; Xiao, Jie; Liu, Jun

    2015-04-01

    Nitrogen-doped porous carbon (NPC) and multi-wall carbon nanotube (MWCNT) have been frequently studied to immobilize sulfur in lithium-sulfur (Li-S) batteries. However, neither NPC nor MWCNT itself can effectively confine the soluble polysufides if cathode thickness e.g. sulfur loading is increased. In this work, NPC was combined with MWCNT to construct an integrated host structure to immobilize sulfur at a relevant scale. The function of doped nitrogen atoms was revisited and found to effectively attract sulfur radicals generated during the electrochemical process. The addition of MWCNT facilitated the uniform coating of sulfur nanocomposites to a practically usable thickness and homogenized the distribution of sulfur particles in the pristine electrodes, while NPC provided sufficient pore volume to trap dissolved species. More importantly, the wetting issue, the critical challenge for thick sulfur cathodes, is also mitigated after the adoption of MWCNT, leading to a high areal capacity of ca. 2.5 mAh/cm2 with capacity retention of 81.6% over 100 cycles

  7. Simultaneous fluorination of active material and conductive agent for improving the electrochemical performance of LiNi0.5Mn1.5O4 electrode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Song, Min Sang; Kim, Dae Sik; Park, Eunjun; Choi, Jae Man; Kim, Hansu

    2016-09-01

    High-voltage cathode materials have gained much attention as one of the promising electrode materials to increase power density of lithium ion batteries by raising the working voltage. However, the use of such high-voltage cathode materials is still challenging, because their working voltage is close to the electrochemical oxidation potential of organic electrolyte used in lithium ion batteries. In this work, we demonstrated that simultaneous fluorination of LiNi0.5Mn1.5O4 (LNMO) particles as well as conductive agent in the electrode could significantly improve the electrochemical stability of LNMO cathode. The resulting electrode showed better cycle performance both at room temperature and elevated temperature compared to both bare LNMO electrode and the electrode with only LNMO fluorinated. These results showed that direct fluorination of high voltage cathode can reduce the side reaction of high voltage cathode electrode with the electrolyte, thereby stabilizing the surface of carbon black as well as that of high voltage cathode material.

  8. Binary iron-chromium oxide as negative electrode for lithium-ion micro-batteries - spectroscopic and microscopic characterization

    NASA Astrophysics Data System (ADS)

    Tian, Bingbing; Światowska, Jolanta; Maurice, Vincent; Zanna, Sandrine; Seyeux, Antoine; Marcus, Philippe

    2015-10-01

    (Fe,Cr)-binary oxide thin film electrodes were prepared as negative electrode material for lithium-ion micro-batteries by thermal growth on a stainless steel (AISI 410, FeCr12.5) current collector. The mechanisms of lithiation/delithiation were investigated by means of electrochemical (CV, galvanostatic cycling), spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical techniques. The as-prepared (Fe, Cr)-binary oxide electrodes exhibit a good cycling performance except the first discharge/charge cycle where a high irreversible capacity is observed due to formation of a solid electrolyte interphase (SEI) layer. The influence of substituting an oxidized iron by an oxidized chromium (CrxFe2-xO3 phase) was evaluated. The data show that the inferior electrochemical conversion activity of substituted oxidized chromium results in hindering lithium transport in the bulk thin film electrode. It was observed that the irreversible morphology modifications together with SEI evolution are critical to capacity degradation while retaining good coulombic efficiency.

  9. Combined NMR and PDF studies of positive electrode materials for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Breger, Julien

    Layered lithium nickel manganese oxides are promising, inexpensive and nontoxic alternative positive electrodes materials to the commercial LiCoO 2 electrode used in Li-ion batteries. Among these materials, Li(NiMn) 0.5O2 is particularly attractive due to its high theoretical capacity (280 mAh/g). The motivation for the research presented here was to understand the detailed long-range and short-range structure of these materials, particularly Li(NiMn)0.5O2, both as-synthesised and upon cycling. It is indeed important to know what the cation environments are, especially for the Li ions, since they strongly affect the electrochemical performance. The local environments and short-range ordering of Li(NiMn)0.5O 2, a potential Li-ion battery positive electrode material, were investigated by using a combination of X-ray and neutron diffraction and isotopic substitution (NDIS) techniques, 6Li Magic Angle Spinning (MAS) NMR spectroscopy and, for the first time, X-ray and neutron Pair Distribution Function (PDF) analysis, associated with Reverse Monte Carlo (RMC) calculations. Two Li(NiMn) 0.5O2 samples were studied in detail: one obtained from regular solid-state synthesis (SS), and another one obtained from ion-exchange routes (IE). 6Li MAS NMR experiments showed less Li/Ni site exchange (between the Li and the Ni/Mn layers) for the IE compound than for the SS compound, explaining its improved Li diffusivity and rate capability. For the SS compound, the Ni/Ni and Mn/Mn repulsion seen by PDF/RMC and the Li/Mn proximity seen by NMR were consistent with an ordering scheme intermediate between the ideal structures proposed so far (the "honey-comb" and "flower" structures). Ordering of Ni and Mn atoms in the transition metal layers was also detected in IE-Li(NiMn)0.5O2: Ni atoms tend to be surrounded by more Mn atoms in the first coordination shell, while the second coordination shell shows that zigzag ordering scheme is preferred over the chain. Ex-situ neutron diffraction

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

    NASA Astrophysics Data System (ADS)

    Jiang, Meng

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

  11. Application of a bio-derivative, rosin, as a binder additive for lithium titanium oxide electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, So-Jin; Lee, Bo-Ram; Oh, Eun-Suok

    2015-01-01

    Rosin, which is an extract of pine trees, is used as an eco-friendly binder additive to a conventional solvent-based binder, polyvinylidene fluoride (PVdF). The composite binder system is used to evaluate the performance of the Li4Ti5O12 (LTO) electrodes using a range of physical and electrochemical characterization techniques. The addition of rosin decreases the crystallinity of PVdF, disperses the conducting agent and binder well, and ultimately leads to an increase in the diffusivity and cyclic capacity of lithium ions. When the amount of rosin additive to the PVdF binder is 40 wt%, the LTO electrode exhibits the highest cyclic capacity and diffusivity; of 164 mAh g-1 at the 110th cycle and 4.28 × 10-10 cm2 s-1, respectively.

  12. Manufacturing of industry-relevant silicon negative composite electrodes for lithium ion-cells

    NASA Astrophysics Data System (ADS)

    Nguyen, B. P. N.; Chazelle, S.; Cerbelaud, M.; Porcher, W.; Lestriez, B.

    2014-09-01

    In this paper, Poly (acrylic-co-maleic) acid (PAMA) is used as a dispersant to improve the stability of electrodes slurries for large scale processing of Silicon based negative composite electrode. The stability and homogeneity of the slurries are characterized using different techniques. Sedimentation test, electrical measurement, SEM-EDX observations as well as rheological measurements show that a more homogeneous distribution of carbon black (CB) inside the stack of Si particles is reached with presence of PAMA. However, the amount of PAMA is limited due to the competition in the adsorption of PAMA and Carboxylmethyl cellulose (CMC) at the surface of the CB particles. Upon cycling with capacity limitation, the optimized electrode formulation at lab scale could achieve more than 400 cycles with surface capacity ∼2.5-3.3 mAh cm-2. At the pilot scale, the improvement of adhesion of the tape to the current collector by using Styrene-co-Butadiene rubber copolymer latex (SB) helps to maintain long cycle life while calendaring is detrimental to electrochemical properties.

  13. Multilayer Interconnects for Microfabricated Surface Electrode Ion Traps

    NASA Astrophysics Data System (ADS)

    Amini, Jason; Seidelin, Signe; Wesenberg, Janus; Britton, Joe; Blakestad, Brad; Brown, Kenton; Epstein, Ryan; Home, Jonathan; Jost, John; Langer, Chris; Leibfried, Dietrich; Ozeri, Roee; Wineland, David

    2007-06-01

    Microfabricated surface electrode traps for ions are a promising technology for building scalable trapping geometries for quantum information processing. We have expanded upon our single layer gold-on-fused-silica surface electrode trap [1] to include a second patterned conducting layer under the trapping electrodes and have demonstrated the fabrication of this architecture using standard microfabrication techniques. The multilayer approach allows for a significant increase in multi-zone trapping complexity and permits improved trapping structures that are otherwise unattainable in single layer designs without vertical interconnects through the wafer. Using improved calculational methods [2], we are in the process of optimizing the planar designs to create modular elements that can be joined into larger multi-zone trapping structures. Work supported by DTO and NIST. 1. S. Seidelin et al., Phys. Rev. Lett. 96, 253003 (2006). Also, see the abstract by S. Seidelin. 2. See the abstract by J. H. Wesenberg.

  14. Importance of open pore structures with mechanical integrity in designing the cathode electrode for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Kim, C.-S.; Guerfi, A.; Hovington, P.; Trottier, J.; Gagnon, C.; Barray, F.; Vijh, A.; Armand, M.; Zaghib, K.

    2013-11-01

    The robustness of conductive networks and the accessibility of electrolyte into the network are important factors in designing the cathode electrode for lithium/sulfur (Li/S) batteries containing liquid electrolytes that involve liquid phase electrochemical reactions. We show that the performance of Li/S cells can be significantly improved by simply optimizing the electrode processing conditions to have open pore structures and mechanical integrity of the electrode architecture. It is demonstrated that the capacity of 1000 mAh g-1 at 0.1 C and the stable capacity retention of >700 mAh g-1 after 200 cycles at 0.5 C can be achieved with relatively high sulfur content of 68%. 417 Wh kg-1 in specific energy and 623 Wh l-1 in energy density are achievable with this new technology.

  15. A new class of lithium and sodium rechargeable batteries based on selenium and selenium-sulfur as a positive electrode.

    PubMed

    Abouimrane, Ali; Dambournet, Damien; Chapman, Karena W; Chupas, Peter J; Weng, Wei; Amine, Khalil

    2012-03-14

    A new class of selenium and selenium-sulfur (Se(x)S(y))-based cathode materials for room temperature lithium and sodium batteries is reported. The structural mechanisms for Li/Na insertion in these electrodes were investigated using pair distribution function (PDF) analysis. Not only does the Se electrode show promising electrochemical performance with both Li and Na anodes, but the additional potential for mixed Se(x)S(y) systems allows for tunable electrodes, combining the high capacities of S-rich systems with the high electrical conductivity of the d-electron containing Se. Unlike the widely studied Li/S system, both Se and Se(x)S(y) can be cycled to high voltages (up to 4.6 V) without failure. Their high densities and voltage output offer greater volumetric energy densities than S-based batteries, opening possibilities for new energy storage systems that can enable electric vehicles and smart grids. PMID:22364225

  16. Exploring the interaction between lithium ion and defective graphene surface using dispersion corrected DFT studies

    SciTech Connect

    Vijayakumar, M.; Hu, Jian Z.

    2013-10-15

    To analyze the lithium ion interaction with realistic graphene surfaces, we carried out dispersion corrected DFT-D3 studies on graphene with common point defects and chemisorbed oxygen containing functional groups along with defect free graphene surface. Our study reveals that, the interaction between lithium ion (Li+) and graphene is mainly through the delocalized π electron of pure graphene layer. However, the oxygen containing functional groups pose high adsorption energy for lithium ion due to the Li-O ionic bond formation. Similarly, the point defect groups interact with lithium ion through possible carbon dangling bonds and/or cation-π type interactions. Overall these defect sites render a preferential site for lithium ions compared with pure graphene layer. Based on these findings, the role of graphene surface defects in lithium battery performance were discussed.

  17. Lithium

    MedlinePlus

    ... bipolar disorder (manic-depressive disorder; a disease that causes episodes of depression, episodes of mania, and other abnormal moods). Lithium ... Lithium is also sometimes used to treat depression, schizophrenia (a mental ... emotions), disorders of impulse control (inability to resist the urge ...

  18. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

    PubMed Central

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

  19. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

    DOE PAGESBeta

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; et al

    2016-04-05

    Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

  20. Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

    PubMed Central

    Blinn, Kevin S.; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A.; Liu, Meilin

    2012-01-01

    Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM

  1. A finite element simulation on transient large deformation and mass diffusion in electrodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    An, Yonghao; Jiang, Hanqing

    2013-10-01

    Lithium-ion batteries have attracted great deal of attention recently. Silicon is one of the most promising anode materials for high-performance lithium-ion batteries, due to its highest theoretical specific capacity. However, the short lifetime confined by mechanical failure in the silicon anode is now considered to be the biggest challenge in desired applications. High stress induced by the huge volume change due to lithium insertion/extraction is the main reason underlying this problem. Some theoretical models have been developed to address this issue. In order to properly implement these models, we develop a finite element based numerical method using a commercial software package, ABAQUS, as a platform at the continuum level to study fully coupled large deformation and mass diffusion problem. Using this method, large deformation, elasticity-plasticity of the electrodes, various spatial and temporal conditions, arbitrary geometry and dimension could be fulfilled. The interaction between anode and other components of the lithium ion batteries can also be studied as an integrated system. Several specific examples are presented to demonstrate the capability of this numerical platform.

  2. Surface-Plasmon Enhanced Transparent Electrodes in Organic Photovoltaics

    SciTech Connect

    Reilly III, T. H.; van de Lagemaat, J.; Tenent, R. C.; Morfa, A. J.; Rowlen, K. L.

    2008-01-01

    Random silver nanohole films were created through colloidal lithography techniques and metal vapor deposition. The transparent electrodes were characterized by uv-visible spectroscopy and incorporated into an organic solar cell. The test cells were evaluated for solar power-conversion efficiency and incident photon-to-current conversion efficiency. The incident photon-to-current conversion efficiency spectra displayed evidence that a nanohole film with 92 nm diameter holes induces surface-plasmon-enhanced photoconversion. The nanohole silver films demonstrate a promising route to removing the indium tin oxide transparent electrode that is ubiquitous in organic optoelectronics.

  3. Design Optimization for Anharmonic Linear Surface-Electrode Ion Trap

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Chen, Shu-Ming; Chen, Ping-Xing; Wu, Wei

    2014-11-01

    An accurate and rapid method is proposed to optimize anharmonic linear surface-electrode ion trap design. Based on the method, we analyze the impact of the architectural parameters, including the width, number, and applied voltage of prerequisite active electrodes, on the number and spacing of trapped ions. Sets of optimal anharmonic trap design are given. Then the optimal designs are verified by using an ant colony optimization algorithm. The results show that the maximum ion position errors and maximum ion spacing errors are less than 1 μm up to 80. The mean of the maximum errors is nearly linear with respect to the number of trapped ions.

  4. Investigation of processes involved in the formation of the solid electrolyte interphase layer during the primary lithiation of the negative electrode for a lithium ion capacitor

    NASA Astrophysics Data System (ADS)

    Gourdin, Gerald T.

    Electrochemically-driven lithiation of an amorphous carbon electrode was evaluated under three configurations: unaided, lithium facing carbon (front-side), and lithium facing current collector (back-side). The results showed that electrochemically-driven pre-lithiation in the front-side configuration produced reversible capacities that were comparable to unaided lithiation, while the back-side configuration produced loading capacities that were approximately 95% of the loading capacities obtained in the front-side configuration. During lithiation of the negative carbon electrode, the electrolyte reacts with the electrode surface and undergoes decomposition to form a solid electrolyte interphase (SEI) layer that passivates the surface of the carbon electrode. The complex reduction reactions that the solvent undergoes will also generate gaseous and electrolyte-soluble products and they will also have a significant affect on the performance of the device. During the primary lithiation process of an amorphous carbon electrode, the changes in the composition of the gas phase and the electrolyte was systematically determined at different cell potential stages through the use of in-situ electrochemical-MS analyses. These analyses were correlated with supporting analyses of the SEI layer itself using the DRIFTS and EIS techniques. The results from the gas phase analysis showed that the decomposition reactions that result in SEI layer formation and the generation of decomposition gasses occurs after two reduction steps at different cell potentials and that it is only after the second step are the decomposition gasses generated. LC-MS analyses were used to separate the electrolyte-soluble decomposition products and it was concluded that their formation are the result of other electrochemical processes occurring in the same cell potential range as the first reduction step. A detailed analysis of the mass spectra from each of these compounds first led an elucidation of

  5. Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

    NASA Technical Reports Server (NTRS)

    Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

    2008-01-01

    Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

  6. Transition Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium and Sodium Ion Batteries with Excellent Cycling Properties

    SciTech Connect

    Sougrati, M. T.; Darwiche, Ali; Liu, Xiaohiu; Mahmoud, A.; Hermann, Raphael P; Jouen, Samuel; Monconduit, Laure; Dronskowski, Richard; Stievano, L.

    2016-01-01

    We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides Mx(NCN)y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performances open the way to the design of a novel family of anode materials.

  7. Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

    DOE PAGESBeta

    Sougrati, Moulay T.; Darwiche, Ali; Liu, Xiaohiu; Mahmoud, Abdelfattah; Hermann, Raphael P.; Jouen, Samuel; Monconduit, Laure; Dronskowski, Richard; Stievano, Lorenzo

    2016-03-16

    Here we report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not requiremore » heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g-1 for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides Mx(NCN)y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Ultimately, their electrochemical activity and performances open the way to the design of a novel family of anode materials.« less

  8. Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties.

    PubMed

    Sougrati, Moulay T; Darwiche, Ali; Liu, Xiaohiu; Mahmoud, Abdelfattah; Hermann, Raphael P; Jouen, Samuel; Monconduit, Laure; Dronskowski, Richard; Stievano, Lorenzo

    2016-04-11

    We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on (57)Fe Mössbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe-NCN into Li/Na-NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (such as nanoscale tailoring, sophisticated textures, or coating) to obtain long cycle life with current density as high as 9 A g(-1) for hundreds of charge-discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M(x)(NCN)y with M=Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performance open the way to the design of a novel family of anode materials. PMID:26989882

  9. Hot-rolling nanowire transparent electrodes for surface roughness minimization

    PubMed Central

    2014-01-01

    Silver nanowire transparent electrodes are a promising alternative to transparent conductive oxides. However, their surface roughness presents a problem for their integration into devices with thin layers such as organic electronic devices. In this paper, hot rollers are used to soften plastic substrates with heat and mechanically press the nanowires into the substrate surface. By doing so, the root-mean-square surface roughness is reduced to 7 nm and the maximum peak-to-valley value is 30 nm, making the electrodes suitable for typical organic devices. This simple process requires no additional materials, which results in a higher transparency, and is compatible with roll-to-roll fabrication processes. In addition, the adhesion of the nanowires to the substrate significantly increases. PMID:24994963

  10. Hot-rolling nanowire transparent electrodes for surface roughness minimization

    NASA Astrophysics Data System (ADS)

    Hosseinzadeh Khaligh, Hadi; Goldthorpe, Irene A.

    2014-06-01

    Silver nanowire transparent electrodes are a promising alternative to transparent conductive oxides. However, their surface roughness presents a problem for their integration into devices with thin layers such as organic electronic devices. In this paper, hot rollers are used to soften plastic substrates with heat and mechanically press the nanowires into the substrate surface. By doing so, the root-mean-square surface roughness is reduced to 7 nm and the maximum peak-to-valley value is 30 nm, making the electrodes suitable for typical organic devices. This simple process requires no additional materials, which results in a higher transparency, and is compatible with roll-to-roll fabrication processes. In addition, the adhesion of the nanowires to the substrate significantly increases.

  11. Effects of electrode surface structure on the mechanoelectrical transduction of IPMC sensors

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Pugal, David; Kim, Kwang

    2014-03-01

    This study investigates the effects of electrode surface structure on the mechanoelectrical transduction of IPMC sensors. A physics-based mechanoelectrical transduction model was developed that takes into account the electrode surface profile (shape) by describing the polymer-electrode interface as a Koch fractal structure. Based on the model, the electrode surface effects were experimentally investigated in case of IPMCs with Pd-Pt electrodes. IPMCs with different electrode surface structures were fabricated through electroless plating process by appropriately controlling the synthesis parameters and conditions. The changes in the electrode surface morphology and the corresponding effects on the IPMC mechanoelectrical transduction were examined. Our experimental results indicate that increasing the dispersion of Pd particles near the membrane surface, and thus the polymer-electrode interfacial area, leads to a higher peak mechanoelectrically induced voltage of IPMC. However, the overall effect of the electrode surface structure is relatively low compared to the electromechanical transduction, which is in good agreement with theoretical prediction.

  12. Lithium Surface Coatings for Improved Plasma Performance in NSTX

    SciTech Connect

    Kugel, H W; Ahn, J -W; Allain, J P; Bell, R; Boedo, J; Bush, C; Gates, D; Gray, T; Kaye, S; Kaita, R; LeBlanc, B; Maingi, R; Majeski, R; Mansfield, D; Menard, J; Mueller, D; Ono, M; Paul, S; Raman, R; Roquemore, A L; Ross, P W; Sabbagh, S; Schneider, H; Skinner, C H; Soukhanovskii, V; Stevenson, T; Timberlake, J; Wampler, W R

    2008-02-19

    NSTX high-power divertor plasma experiments have shown, for the first time, significant and frequent benefits from lithium coatings applied to plasma facing components. Lithium pellet injection on NSTX introduced lithium pellets with masses 1 to 5 mg via He discharges. Lithium coatings have also been applied with an oven that directed a collimated stream of lithium vapor toward the graphite tiles of the lower center stack and divertor. Lithium depositions from a few mg to 1 g have been applied between discharges. Benefits from the lithium coating were sometimes, but not always seen. These improvements sometimes included decreases plasma density, inductive flux consumption, and ELM frequency, and increases in electron temperature, ion temperature, energy confinement and periods of MHD quiescence. In addition, reductions in lower divertor D, C, and O luminosity were measured.

  13. Solid solution lithium alloy cermet anodes

    DOEpatents

    Richardson, Thomas J.

    2013-07-09

    A metal-ceramic composite ("cermet") has been produced by a chemical reaction between a lithium compound and another metal. The cermet has advantageous physical properties, high surface area relative to lithium metal or its alloys, and is easily formed into a desired shape. An example is the formation of a lithium-magnesium nitride cermet by reaction of lithium nitride with magnesium. The reaction results in magnesium nitride grains coated with a layer of lithium. The nitride is inert when used in a battery. It supports the metal in a high surface area form, while stabilizing the electrode with respect to dendrite formation. By using an excess of magnesium metal in the reaction process, a cermet of magnesium nitride is produced, coated with a lithium-magnesium alloy of any desired composition. This alloy inhibits dendrite formation by causing lithium deposited on its surface to diffuse under a chemical potential into the bulk of the alloy.

  14. 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.

  15. High surface area, low weight composite nickel fiber electrodes

    NASA Technical Reports Server (NTRS)

    Johnson, Bradley A.; Ferro, Richard E.; Swain, Greg M.; Tatarchuk, Bruce J.

    1993-01-01

    The energy density and power density of light weight aerospace batteries utilizing the nickel oxide electrode are often limited by the microstructures of both the collector and the resulting active deposit in/on the collector. Heretofore, these two microstructures were intimately linked to one another by the materials used to prepare the collector grid as well as the methods and conditions used to deposit the active material. Significant weight and performance advantages were demonstrated by Britton and Reid at NASA-LeRC using FIBREX nickel mats of ca. 28-32 microns diameter. Work in our laboratory investigated the potential performance advantages offered by nickel fiber composite electrodes containing a mixture of fibers as small as 2 microns diameter (Available from Memtec America Corporation). These electrode collectors possess in excess of an order of magnitude more surface area per gram of collector than FIBREX nickel. The increase in surface area of the collector roughly translates into an order of magnitude thinner layer of active material. Performance data and advantages of these thin layer structures are presented. Attributes and limitations of their electrode microstructure to independently control void volume, pore structure of the Ni(OH)2 deposition, and resulting electrical properties are discussed.

  16. Lithium-based surfaces controlling fusion plasma behavior at the plasma-material interface

    SciTech Connect

    Allain, Jean Paul; Taylor, Chase N.

    2012-05-15

    The plasma-material interface and its impact on the performance of magnetically confined thermonuclear fusion plasmas are considered to be one of the key scientific gaps in the realization of nuclear fusion power. At this interface, high particle and heat flux from the fusion plasma can limit the material's lifetime and reliability and therefore hinder operation of the fusion device. Lithium-based surfaces are now being used in major magnetic confinement fusion devices and have observed profound effects on plasma performance including enhanced confinement, suppression and control of edge localized modes (ELM), lower hydrogen recycling and impurity suppression. The critical spatial scale length of deuterium and helium particle interactions in lithium ranges between 5-100 nm depending on the incident particle energies at the edge and magnetic configuration. Lithium-based surfaces also range from liquid state to solid lithium coatings on a variety of substrates (e.g., graphite, stainless steel, refractory metal W/Mo/etc., or porous metal structures). Temperature-dependent effects from lithium-based surfaces as plasma facing components (PFC) include magnetohydrodynamic (MHD) instability issues related to liquid lithium, surface impurity, and deuterium retention issues, and anomalous physical sputtering increase at temperatures above lithium's melting point. The paper discusses the viability of lithium-based surfaces in future burning-plasma environments such as those found in ITER and DEMO-like fusion reactor devices.

  17. Solid Electrolyte Lithium Phosphous Oxynitride as a Protective Nanocladding Layer for 3D High-Capacity Conversion Electrodes.

    PubMed

    Lin, Chuan-Fu; Noked, Malachi; Kozen, Alexander C; Liu, Chanyuan; Zhao, Oliver; Gregorczyk, Keith; Hu, Liangbing; Lee, Sang Bok; Rubloff, Gary W

    2016-02-23

    Materials that undergo conversion reactions to form different materials upon lithiation typically offer high specific capacity for energy storage applications such as Li ion batteries. However, since the reaction products often involve complex mixtures of electrically insulating and conducting particles and significant changes in volume and phase, the reversibility of conversion reactions is poor, preventing their use in rechargeable (secondary) batteries. In this paper, we fabricate and protect 3D conversion electrodes by first coating multiwalled carbon nanotubes (MWCNT) with a model conversion material, RuO2, and subsequently protecting them with conformal thin-film lithium phosphous oxynitride (LiPON), a well-known solid-state electrolyte. Atomic layer deposition is used to deposit the RuO2 and the LiPON, thus forming core double-shell MWCNT@RuO2@LiPON electrodes as a model system. We find that the LiPON protection layer enhances cyclability of the conversion electrode, which we attribute to two factors. (1) The LiPON layer provides high Li ion conductivity at the interface between the electrolyte and the electrode. (2) By constraining the electrode materials mechanically, the LiPON protection layer ensures electronic connectivity and thus conductivity during lithiation/delithiation cycles. These two mechanisms are striking in their ability to preserve capacity despite the profound changes in structure and composition intrinsic to conversion electrode materials. This LiPON-protected structure exhibits superior cycling stability and reversibility as well as decreased overpotentials compared to the unprotected core-shell structure. Furthermore, even at very low lithiation potential (0.05 V), the LiPON-protected electrode largely reduces the formation of a solid electrolyte interphase. PMID:26820038

  18. Charge-discharge characteristics of natural graphite electrode in N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)amide containing lithium ion for lithium-ion secondary batteries

    NASA Astrophysics Data System (ADS)

    Towada, Jun; Karouji, Tomohiro; Sato, Hiroki; Kadoma, Yoshihiro; Shimada, Kazuaki; Ui, Koichi

    2015-02-01

    We investigated the electrochemical characteristics of a natural graphite electrode in room-temperature ionic liquids not containing additives. N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)amide (DEME-TFSA) containing lithium bis(trifluoromethylsulfonyl)amide (Li-TFSA) as the electrolyte and a natural graphite electrode as the negative electrode material were employed. The charge-discharge tests showed that the discharge capacity and the charge-discharge efficiency of the natural graphite electrode at the 1st cycle were 318 mAh g-1 and 75.6%, respectively. The cycle performance showed that the discharge capacity and the charge-discharge efficiency were stably maintained at ca. 320 mAh g-1 and 100%, respectively, until the initial 10th cycle. The ex-situ X-ray diffraction measurements showed that lithium-graphite intercalation compounds, such as LiC12 and LiC6, were formed after the 1st charge. The structural change in the natural graphite electrode was reversible because graphite recovered to its original structure after the 1st discharge. These results clarified that the graphite electrode could operate as a negative electrode for lithium-ion secondary batteries in DEME-TFSA containing Li-TFSA without organic solvents.

  19. High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure

    PubMed Central

    Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu; Shiiba, Hiromasa; Ogawa, Masahiro; Nakayama, Keisuke; Ohta, Toshiaki; Endo, Daisuke; Ozaki, Tetsuya; Inamasu, Tokuo; Sato, Kei; Komaba, Shinichi

    2015-01-01

    Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn4+, Ru4+, etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co3+, Ni3+, etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh⋅g−1 of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions. PMID:26056288

  20. High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure.

    PubMed

    Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu; Shiiba, Hiromasa; Ogawa, Masahiro; Nakayama, Keisuke; Ohta, Toshiaki; Endo, Daisuke; Ozaki, Tetsuya; Inamasu, Tokuo; Sato, Kei; Komaba, Shinichi

    2015-06-23

    Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn(4+), Ru(4+), etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co(3+), Ni(3+), etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh ⋅ g(-1) of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions. PMID:26056288

  1. Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures.

    PubMed

    Huang, Cheng; Xiao, Jie; Shao, Yuyan; Zheng, Jianming; Bennett, Wendy D; Lu, Dongping; Saraf, Laxmikant V; Engelhard, Mark; Ji, Liwen; Zhang, Jiguang; Li, Xiaolin; Graff, Gordon L; Liu, Jun

    2014-01-01

    Lithium-sulphur batteries have high theoretical energy density and potentially low cost, but significant challenges such as severe capacity degradation prevent its widespread adoption. Here we report a new design of lithium-sulphur battery using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on lithium. Lithiated graphite placed in front of the lithium metal functions as an artificial, self-regulated solid electrolyte interface layer to actively control the electrochemical reactions and minimize the deleterious side reactions, leading to significant performance improvements. Lithium-sulphur cells incorporating this hybrid anodes deliver capacities of >800 mAh g(-1) for 400 cycles at a high rate of 1,737 mA g(-1), with only 11% capacity fade and a Coulombic efficiency >99%. This simple hybrid concept may also provide scientific strategies for protecting metal anodes in other energy-storage devices. PMID:24402522

  2. Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures

    SciTech Connect

    Huang, C; Xiao, J; Shao, YY; Zheng, JM; Bennett, WD; Lu, DP; Saraf, LV; Engelhard, M; Ji, LW; Zhang, J; Li, XL; Graff, GL; Liu, J

    2014-01-09

    Lithium-sulphur batteries have high theoretical energy density and potentially low cost, but significant challenges such as severe capacity degradation prevent its widespread adoption. Here we report a new design of lithium-sulphur battery using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on lithium. Lithiated graphite placed in front of the lithium metal functions as an artificial, self-regulated solid electrolyte interface layer to actively control the electrochemical reactions and minimize the deleterious side reactions, leading to significant performance improvements. Lithium-sulphur cells incorporating this hybrid anodes deliver capacities of >800 mAhg(-1) for 400 cycles at a high rate of 1,737mAg(-1), with only 11% capacity fade and a Coulombic efficiency >99%. This simple hybrid concept may also provide scientific strategies for protecting metal anodes in other energy-storage devices.

  3. Cryogenic ion trapping systems with surface-electrode traps

    NASA Astrophysics Data System (ADS)

    Antohi, P. B.; Schuster, D.; Akselrod, G. M.; Labaziewicz, J.; Ge, Y.; Lin, Z.; Bakr, W. S.; Chuang, I. L.

    2009-01-01

    We present two simple cryogenic rf ion trap systems in which cryogenic temperatures and ultra high vacuum pressures can be reached in as little as 12 h. The ion traps are operated either in a liquid helium bath cryostat or in a low vibration closed cycle cryostat. The fast turn around time and availability of buffer gas cooling made the systems ideal for testing surface-electrode ion traps. The vibration amplitude of the closed cycled cryostat was found to be below 106 nm. We evaluated the systems by loading surface-electrode ion traps with S88r+ ions using laser ablation, which is compatible with the cryogenic environment. Using Doppler cooling we observed small ion crystals in which optically resolved ions have a trapped lifetime over 2500 min.

  4. LiCoO2 and SnO2 Thin Film Electrodes for Lithium-Ion Battery Applications

    NASA Technical Reports Server (NTRS)

    Maranchi, Jeffrey P.; Hepp, Aloysius F.; Kumta, Prashant N.

    2004-01-01

    There is an increasing need for small dimension, ultra-lightweight, portable power supplies due to the miniaturization of consumer electronic devices. Rechargeable thin film lithium-ion batteries have the potential to fulfill the growing demands for micro-energy storage devices. However, rechargeable battery technology and fabrication processes have not kept paced with the advances made in device technology. Economical fabrication methods lending excellent microstructural and compositional control in the thin film battery electrodes have yet to be fully developed. In this study, spin coating has been used to demonstrate the flexibility of the approach to produce both anode (SnO2) and cathode (LiCoO2) thin films. Results on the microstructure crystal structure and electrochemical properties of the thin film electrodes are described and discussed.

  5. In Situ Radiographic Investigation of (De)Lithiation Mechanisms in a Tin-Electrode Lithium-Ion Battery.

    PubMed

    Sun, Fu; Markötter, Henning; Zhou, Dong; Alrwashdeh, Saad Sabe Sulaiman; Hilger, Andre; Kardjilov, Nikolay; Manke, Ingo; Banhart, John

    2016-05-10

    The lithiation and delithiation mechanisms of multiple-Sn particles in a customized flat radiography cell were investigated by in situ synchrotron radiography. For the first time, four (de)lithiation phenomena in a Sn-electrode battery system are highlighted: 1) the (de)lithiation behavior varies between different Sn particles, 2) the time required to lithiate individual Sn particles is markedly different from the time needed to discharge the complete battery, 3) electrochemical deactivation of originally electrochemically active particles is reported, and 4) a change of electrochemical behavior of individual particles during cycling is found and explained by dynamic changes of (de)lithiation pathways amongst particles within the electrode. These unexpected findings fundamentaly expand the understanding of the underlying (de)lithiation mechanisms inside commercial lithium-ion batteries (LIBs) and would open new design principles for high-performance next-generation LIBs. PMID:27076373

  6. Evaluation of lithium ion cells with titanate negative electrodes and iron phosphate positive electrode for start-stop applications

    NASA Astrophysics Data System (ADS)

    Wang, John S.; Liu, Ping; Soukiazian, Souren; Tataria, Harshad; Dontigny, Martin; Guerfi, Abdelbast; Zaghib, Karim; Verbrugge, Mark W.

    2014-06-01

    Start-stop systems require the battery to provide high power, endure shallow cycling, and exhibit long cycle life. The LFP/LTO (lithium iron phosphate/lithium titanate) battery is a potential candidate to meet such requirements because, at room temperature, both materials can be operated at high rate and have good stability (calendar and cycle life). In this work, we have investigated the feasibility of using LixFePO4/Li4+3yTi5O12 (0 < x < 1, 0 < y < 1) lithium ion batteries for start-stop systems. We evaluate both the rate and temperature dependence of LFP/LTO cells subjected to galvanostatic charge/discharge cycling. Excellent rate performance was observed at temperatures above or at ambient. However, at low temperatures, significant resistance is observed, and this must be addressed for the LFP/LTO system to be viable. In addition, we investigate the SOC dependence of equivalent circuit parameters using triangular current and voltage excitation method to facilitate the implementation of circuit-based control algorithms for vehicle applications. Parameter values are nearly constant over the broad voltage-plateau region of the substantially two-phase behavior of both the LFP and LTO materials.

  7. Effect of the specific surface area on thermodynamic and kinetic properties of nanoparticle anatase TiO2 in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Madej, Edyta; Klink, Stefan; Schuhmann, Wolfgang; Ventosa, Edgar; La Mantia, Fabio

    2015-11-01

    Anatase TiO2 nanoparticles with a specific surface area of 100 m2 g-1 and 300 m2 g-1 have been investigated as negative insertion electrode material for lithium-ion batteries. Galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS) were used to investigate the effect of the specific surface area on the performance of the material. GITT was performed at C/10 rate, followed by an EIS measurement after each relaxation step. Separation of kinetic and thermodynamic contributions to the overpotential of the phase transformation on Li+ (de-)insertion allowed revealing a dependency of both terms on the specific surface area. The material with higher surface area undergoes intrinsic transformation during the initial cycles affecting the thermodynamics of (de-)insertion while the sample with lower surface area shows large and asymmetric kinetic hindrances. For the material with 15 nm particles, Li+ de-insertion appears to have a higher resistance than lithium insertion.

  8. Biomass-Derived Electrode for Next Generation Lithium-Ion Capacitors.

    PubMed

    Sennu, Palanichamy; Aravindan, Vanchiappan; Ganesan, Mahadevan; Lee, Young-Gi; Lee, Yun-Sung

    2016-04-21

    We report the fabrication of a carbon-based high energy density Li-ion hybrid electrochemical capacitor (Li-HEC) from low cost and eco-friendly materials. High surface area (2448±20 m(2)  g(-1) ) activated carbon (AC) is derived from the environmentally threatening plant, Prosopis juliflora, and used as the positive electrode in a Li-HEC assembly. Natural graphite is employed as negative electrode and electrochemically pre-lithiated prior to the Li-HEC fabrication. The Li-HEC delivers a specific energy of 162.3 Wh kg(-1) and exhibits excellent cyclability (i.e., ∼79 % of initial capacity is retained after 7000 cycles). The superior electrochemical performance of Li-HEC benefits from the tube-like unique structural features of the AC. Also, the presence of a graphitic nanocarbon network improves the ion transport, and the formed micro- and meso-porous network acts as reservoir for the accommodation of charge carriers. PMID:26990699

  9. Modeling mass and density distribution effects on the performance of co-extruded electrodes for high energy density lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Cobb, Corie L.; Blanco, Mario

    2014-03-01

    Utilizing an existing macro-homogeneous porous electrode model developed by John Newman, this paper aims to explore the potential energy density gains which can be realized in lithium-ion battery electrodes fabricated with co-extrusion printing technology. This paper conducts an analysis on two-dimensional electrode cross-sections and presents the electrochemical performance results, including calculated volumetric energy capacity for a general class of lithium cobalt oxide (LiCoO2) co-extruded cathodes, in the presence of a lithium metal anode, polymer separator and liquid ethylene carbonate, propylene carbonate, and dimethyl carbonate (EC:PC:DMC) electrolyte. The impact of structured electrodes on cell performance is investigated by varying the physical distribution of a fixed amount of cathode mass over a space of dimensions which can be fabricated by co-extrusion. By systematically varying the thickness and aspect ratio of the electrode structures, we present an optimal subset of geometries and design rules for co-extruded geometries. Modeling results demonstrate that ultra-thick LiCoO2 electrodes, on the order of 150-300 μm, can garner a substantial improvement in material utilization and in turn capacity through electrolyte channels and fine width electrode pillars which are 25-100 μm wide.

  10. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries

    PubMed Central

    2014-01-01

    The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate. PMID:24790684

  11. Carbon electrode with NiO and RuO2 nanoparticles improves the cycling life of non-aqueous lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Tan, P.; Shyy, W.; Wu, M. C.; Huang, Y. Y.; Zhao, T. S.

    2016-09-01

    Carbon has been regarded as one of the most attractive cathode materials for non-aqueous lithium-oxygen batteries due to its excellent conductivity, high specific area, large porosity, and low cost. However, a key disadvantage of carbon electrodes lies in the fact that carbon may react with Li2O2 and electrolyte to form irreversible side products (e.g. Li2CO3) at the active surfaces, leading to a high charge voltage and a short cycling life. In this work, we address this issue by decorating NiO and RuO2 nanoparticles onto carbon surfaces. It is demonstrated that the NiO-RuO2 nanoparticle-decorated carbon electrode not only catalyzes both the oxygen reduction and evolution reactions, but also promotes the decomposition of side products. As a result, the battery fitted with the novel carbon cathode delivers a capacity of 3653 mAh g-1 at a current density of 400 mA g-1, with a charge plateau of 4.01 V. This performance is 440 mV lower than that of the battery fitted with a pristine carbon cathode. The present cathode is also able to operate for 50 cycles without capacity decay at a fixed capacity of 1000 mAh g-1, which is more than twice the cycle number of that of the pristine carbon cathode.

  12. Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach

    SciTech Connect

    Lu, Jun; Zhan, Chun; Wu, Tianpin; Wen, Jianguo; Lei, Yu; Kropf, A. Jeremy; Wu, Huiming; Miller, Dean J.; Elam, Jeffrey W.; Sun, Yang-Kook; Qiu, Xinping; Amine, Khalil

    2014-12-16

    The capacity fade of lithium manganate-based cells is associated with the dissolution of Mn from cathode/electrolyte interface due to the disproportionation reaction of Mn(III), and the subsequent deposition of Mn(II) on the anode. Suppressing the dissolution of Mn from the cathode is critical to reducing capacity fade of LiMn2O4-based cells. Here we report a nanoscale surface-doping approach that minimizes Mn dissolution from lithium manganate. This approach exploits advantages of both bulk doping and surface-coating methods by stabilizing surface crystal structure of lithium manganate through cationic doping while maintaining bulk lithium manganate structure, and protecting bulk lithium manganate from electrolyte corrosion while maintaining ion and charge transport channels on the surface through the electrochemically active doping layer. Consequently, the surface-doped lithium manganate demonstrates enhanced electrochemical performance. This study provides encouraging evidence that surface doping could be a promising alternative to improve the cycling performance of lithium-ion batteries.

  13. Self-assembling synthesis of free-standing nanoporous graphene-transition-metal oxide flexible electrodes for high-performance lithium-ion batteries and supercapacitors.

    PubMed

    Huang, Xiaodan; Sun, Bing; Chen, Shuangqiang; Wang, Guoxiu

    2014-01-01

    The synthesis of nanoporous graphene by a convenient carbon nanofiber assisted self-assembly approach is reported. Porous structures with large pore volumes, high surface areas, and well-controlled pore sizes were achieved by employing spherical silica as hard templates with different diameters. Through a general wet-immersion method, transition-metal oxide (Fe3O4, Co3O4, NiO) nanocrystals can be easily loaded into nanoporous graphene papers to form three-dimensional flexible nanoarchitectures. When directly applied as electrodes in lithium-ion batteries and supercapacitors, the materials exhibited superior electrochemical performances, including an ultra-high specific capacity, an extended long cycle life, and a high rate capability. In particular, nanoporous Fe3O4-graphene composites can deliver a reversible specific capacity of 1427.5 mAh g(-1) at a high current density of 1000 mA g(-1) as anode materials in lithium-ion batteries. Furthermore, nanoporous Co3O4-graphene composites achieved a high supercapacitance of 424.2 F g(-1) . This work demonstrated that the as-developed freestanding nanoporous graphene papers could have significant potential for energy storage and conversion applications. PMID:24129981

  14. DEMS study of gas evolution at thick graphite electrodes for lithium-ion batteries: the effect of γ-butyrolactone

    NASA Astrophysics Data System (ADS)

    Lanz, Martin; Novák, Petr

    Differential electrochemical mass spectrometry (DEMS) was used to study the reductive decomposition of an electrolyte based on ethylene carbonate/dimethyl carbonate (EC/DMC), as well as the formation of a solid electrolyte interphase (SEI) in this electrolyte, at thick (75-100 μm) porous graphite composite electrodes. A number of graphite electrodes differing in their electrochemical lithium intercalation properties were investigated in potential-sweep experiments. They proved to be similar with respect to the evolution of ethylene and hydrogen gas during the first two charge/discharge cycles. Due to an incomplete coulombic conversion, a high irreversible capacity, as well as slow diffusion kinetics and an enhanced ohmic resistance of the electrodes, SEI formation on these thick electrodes was not yet complete after the first charge/discharge cycle. Undesired gas evolution can be reduced by adding γ-butyrolactone (GBL) as an electrolyte co-solvent. The amount of ethylene and hydrogen gas evolved decreases with increasing percentages of GBL in an EC/DMC electrolyte, indicating that the SEI layer is built up from GBL rather than from EC decomposition products.

  15. Electrocatalysis of Lithium Polysulfides: Current Collectors as Electrodes in Li/S Battery Configuration

    PubMed Central

    Babu, Ganguli; Ababtain, Khalid; Ng, K. Y. Simon; Arava, Leela Mohana Reddy

    2015-01-01

    Lithium Sulfur (Li/S) chemistries are amongst the most promising next-generation battery technologies due to their high theoretical energy density. However, the detrimental effects of their intermediate byproducts, polysulfides (PS), have to be resolved to realize these theoretical performance limits. Confined approaches on using porous carbons to entrap PS have yielded limited success. In this study, we deviate from the prevalent approach by introducing catalysis concept in Li/S battery configuration. Engineered current collectors were found to be catalytically active towards PS, thereby eliminating the need for carbon matrix and their processing obligatory binders, additives and solvents. We reveal substantial enhancement in electrochemical performance and corroborate our findings using a detailed experimental parametric study involving variation of several kinetic parameters such as surface area, temperature, current rate and concentration of PS. The resultant novel battery configuration delivered a discharge capacity of 700 mAh g−1 with the two dimensional (2D) planar Ni current collectors and an enhancement in the capacity up to 900 mAh g−1 has been realized using the engineered three dimensional (3D) current collectors. The battery capacity has been tested for stability over 100 cycles of charge-discharge. PMID:25740731

  16. Monodisperse CoFe2O4 nanoparticles supported on Vulcan XC-72: High performance electrode materials for lithium-air and lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Şener, Tansel; Kayhan, Emine; Sevim, Melike; Metin, Önder

    2015-08-01

    Addressed herein is the preparation and the electrode performance of monodisperse CoFe2O4 nanoparticles (NPs) supported on Vulcan XC-72 for the Lithium-air battery (LAB) and Lithium-ion battery (LIB). Monodisperse CoFe2O4 NPs were synthesized by the thermal decomposition of cobalt(II) acetylacetonate and iron(III) acetylacetonate in oleylamine and oleic acid in the presence of 1,2-tetradecanediol and benzyl ether. As-prepared CoFe2O4 NPs with a particle size of 11 nm were then supported on Vulcan XC-72 (Vulcan-CoFe2O4) at different theoretical loadings (20, 40 and 60 wt % CoFe2O4 NPs) by using the simple liquid phase self assembly method. CoFe2O4 NPs dispersed on Vulcan-CoFe2O4 composites were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The AAS analyses indicated that the Vulcan-CoFe2O4 composites with different loadings were included 3.7, 8.1 and 16.4 wt % CoFe2O4 on the metal basis. The electrode performance of Vulcan-CoFe2O4 composites were evaluated as the anode active material for LIB and cathode active material for LABs by performing the galvanostatic charge-discharge tests. The highest discharge capacity for both LAB (7510 mAh g(Vulcan+CoFe2O4)-1; 13380 mAh gCoFe2O4-1 @ 0.1C) and LIB (863 mAh g(Vulcan+CoFe2O4)-1; 9330 mAh gCoFe2O4-1@ 0.1C) was investigated with 16.4 wt % CoFe2O4.

  17. Three-Dimensional Cu2ZnSnS4 Films with Modified Surface for Thin-Film Lithium-Ion Batteries.

    PubMed

    Lin, Jie; Guo, Jianlai; Liu, Chang; Guo, Hang

    2015-08-12

    Cu2ZnSnS4 (CZTS) is an important material in low-cost thin film solar cells and is also a promising candidate for lithium storage. In this work, a novel three-dimensional CZTS film coated with a lithium phosphorus oxynitride (LiPON) film is fabricated for the first time and is applied to thin-film lithium-ion batteries. The modified film exhibits an excellent performance of ∼900 mAh g(-1) (450 μAh cm(-2) μm(-1)), even after 75 cycles. Morphology integrity is still maintained after repeated lithiation/delithiation, and the main reaction mechanism is analyzed in detail. The significant findings from this study indicate the striking advantages of modifying both the surface and structure of alloy-based electrodes for energy storage. PMID:26192026

  18. Layered P3-NaxCo1/3Ni1/3Mn1/3O2 versus Spinel Li4Ti5O12 as a Positive and a Negative Electrode in a Full Sodium-Lithium Cell.

    PubMed

    Ivanova, Svetlana; Zhecheva, Ekaterina; Kukeva, Rositsa; Nihtianova, Diana; Mihaylov, Lyuben; Atanasova, Genoveva; Stoyanova, Radostina

    2016-07-13

    The development of lithium and sodium ion batteries without using lithium and sodium metal as anodes gives the impetus for elaboration of low-cost and environmentally friendly energy storage devices. In this contribution we demonstrate the design and construction of a new type of hybrid sodium-lithium ion cell by using unique electrode combination (Li4Ti5O12 spinel as a negative electrode and layered Na3/4Co1/3Ni1/3Mn1/3O2 as a positive electrode) and conventional lithium electrolyte (LiPF6 salt dissolved in EC/DMC). The cell operates at an average potential of 2.35 V by delivering a reversible capacity of about 100 mAh/g. The mechanism of the electrochemical reaction in the full sodium-lithium ion cell is studied by means of postmortem analysis, as well as ex situ X-ray diffraction analysis, HR-TEM, and electron paramagnetic resonance spectroscopy (EPR). The changes in the surface composition of electrodes are examined by ex situ X-ray photoelectron spectroscopy (XPS). PMID:27315402

  19. Electrical, Mechanical, and Capacity Percolation Leads to High-Performance MoS2/Nanotube Composite Lithium Ion Battery Electrodes.

    PubMed

    Liu, Yuping; He, Xiaoyun; Hanlon, Damien; Harvey, Andrew; Khan, Umar; Li, Yanguang; Coleman, Jonathan N

    2016-06-28

    Advances in lithium ion batteries would facilitate technological developments in areas from electrical vehicles to mobile communications. While two-dimensional systems like MoS2 are promising electrode materials due to their potentially high capacity, their poor rate capability and low cycle stability are severe handicaps. Here, we study the electrical, mechanical, and lithium storage properties of solution-processed MoS2/carbon nanotube anodes. Nanotube addition gives up to 10(10)-fold and 40-fold increases in electrical conductivity and mechanical toughness, respectively. The increased conductivity results in up to a 100× capacity enhancement to ∼1200 mAh/g (∼3000 mAh/cm(3)) at 0.1 A/g, while the improved toughness significantly boosts cycle stability. Composites with 20 wt % nanotubes combine high reversible capacity with excellent cycling stability (e.g., ∼950 mAh/g after 500 cycles at 2 A/g) and high rate capability (∼600 mAh/g at 20 A/g). The conductivity, toughness, and capacity scale with nanotube content according to percolation theory, while the stability increases sharply at the mechanical percolation threshold. We believe that the improvements in conductivity and toughness obtained after addition of nanotubes can be transferred to other electrode materials, such as silicon nanoparticles. PMID:27203558

  20. Facile Preparation and Lithium Storage Properties of TiO2 @Graphene Composite Electrodes with Low Carbon Content.

    PubMed

    Guo, Sheng-Qi; Zhen, Meng-Meng; Liu, Lu; Yuan, Zhi-Hao

    2016-08-16

    Over the past decade, TiO2 /graphene composites as electrodes for lithium ion batteries have attracted a great deal of attention for reasons of safety and environmental friendliness. However, most of the TiO2 /graphene electrodes have large graphene content (9-40 %), which is bound to increase the cost of the battery. Logically, reducing the amount of graphene is a necessary part to achieve a green battery. The synthesis of TiO2 nanosheets under solvothermal conditions without additives is now demonstrated. Through mechanical mixing TiO2 nanosheets with different amount of reduced graphene (rGO), a series of TiO2 @graphene composites was prepared with low graphene content (rGO content 1, 2, 3, and 5 wt %). When these composites were evaluated as anodes for lithium ion batteries, it was found that TiO2 +3 wt % rGO manifested excellent cycling stability and a high specific capacity (243.7 mAh g(-1) at 1 C; 1 C=167.5 mA g(-1) ), and demonstrated superior high-rate discharge/charge capability at 20 C. PMID:27339820

  1. Three dimensional Graphene aerogels as binder-less, freestanding, elastic and high-performance electrodes for lithium-ion batteries

    PubMed Central

    Chen, Zhihang; Li, Hua; Tian, Ran; Duan, Huanan; Guo, Yiping; Chen, Yujie; Zhou, Jie; Zhang, Chunmei; DUGNANI, Roberto; Liu, Hezhou

    2016-01-01

    In this work it is shown how porous graphene aerogels fabricated by an eco-friendly and simple technological process, could be used as electrodes in lithium- ion batteries. The proposed graphene framework exhibited excellent performance including high reversible capacities, superior cycling stability and rate capability. A significantly lower temperature (75 °C) than the one currently utilized in battery manufacturing was utilized for self-assembly hence providing potential significant savings to the industrial production. After annealing at 600 °C, the formation of Sn-C-O bonds between the SnO2 nanoparticles and the reduced graphene sheets will initiate synergistic effect and improve the electrochemical performance. The XPS patterns revealed the formation of Sn-C-O bonds. Both SEM and TEM imaging of the electrode material showed that the three dimensional network of graphene aerogels and the SnO2 particles were distributed homogeneously on graphene sheets. Finally, the electrochemical properties of the samples as active anode materials for lithium-ion batteries were tested and examined by constant current charge–discharge cycling and the finding fully described in this manuscript. PMID:27265146

  2. Three dimensional Graphene aerogels as binder-less, freestanding, elastic and high-performance electrodes for lithium-ion batteries.

    PubMed

    Chen, Zhihang; Li, Hua; Tian, Ran; Duan, Huanan; Guo, Yiping; Chen, Yujie; Zhou, Jie; Zhang, Chunmei; Dugnani, Roberto; Liu, Hezhou

    2016-01-01

    In this work it is shown how porous graphene aerogels fabricated by an eco-friendly and simple technological process, could be used as electrodes in lithium- ion batteries. The proposed graphene framework exhibited excellent performance including high reversible capacities, superior cycling stability and rate capability. A significantly lower temperature (75 °C) than the one currently utilized in battery manufacturing was utilized for self-assembly hence providing potential significant savings to the industrial production. After annealing at 600 °C, the formation of Sn-C-O bonds between the SnO2 nanoparticles and the reduced graphene sheets will initiate synergistic effect and improve the electrochemical performance. The XPS patterns revealed the formation of Sn-C-O bonds. Both SEM and TEM imaging of the electrode material showed that the three dimensional network of graphene aerogels and the SnO2 particles were distributed homogeneously on graphene sheets. Finally, the electrochemical properties of the samples as active anode materials for lithium-ion batteries were tested and examined by constant current charge-discharge cycling and the finding fully described in this manuscript. PMID:27265146

  3. Three dimensional Graphene aerogels as binder-less, freestanding, elastic and high-performance electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, Zhihang; Li, Hua; Tian, Ran; Duan, Huanan; Guo, Yiping; Chen, Yujie; Zhou, Jie; Zhang, Chunmei; Dugnani, Roberto; Liu, Hezhou

    2016-06-01

    In this work it is shown how porous graphene aerogels fabricated by an eco-friendly and simple technological process, could be used as electrodes in lithium- ion batteries. The proposed graphene framework exhibited excellent performance including high reversible capacities, superior cycling stability and rate capability. A significantly lower temperature (75 °C) than the one currently utilized in battery manufacturing was utilized for self-assembly hence providing potential significant savings to the industrial production. After annealing at 600 °C, the formation of Sn-C-O bonds between the SnO2 nanoparticles and the reduced graphene sheets will initiate synergistic effect and improve the electrochemical performance. The XPS patterns revealed the formation of Sn-C-O bonds. Both SEM and TEM imaging of the electrode material showed that the three dimensional network of graphene aerogels and the SnO2 particles were distributed homogeneously on graphene sheets. Finally, the electrochemical properties of the samples as active anode materials for lithium-ion batteries were tested and examined by constant current charge–discharge cycling and the finding fully described in this manuscript.

  4. Mesoporous Li4Ti5O12 nanoclusters anchored on super-aligned carbon nanotubes as high performance electrodes for lithium ion batteries.

    PubMed

    Sun, Li; Kong, Weibang; Wu, Hengcai; Wu, Yang; Wang, Datao; Zhao, Fei; Jiang, Kaili; Li, Qunqing; Wang, Jiaping; Fan, Shoushan

    2016-01-01

    Mesoporous lithium titanate (LTO) nanoclusters are in situ synthesized in a network of super aligned carbon nanotubes (SACNTs) via a solution-based method followed by heat treatment in air. In the LTO-CNT composite, SACNTs not only serve as the skeleton to support a binder-free electrode, but also render the composite with high conductivity, flexibility, and mechanical strength. The homogeneously dispersed LTO nanoclusters among the SACNTs allow each LTO grain to effectively access the electrolyte and the conductive network, benefiting both ion and electron transport. By the incorporation of LTO into the CNT network, mechanical reinforcement is also achieved. When serving as a negative electrode for lithium ion batteries, such a robust composite-network architecture provides the electrodes with effective charge transport and structural integrity, leading to high-performance flexible electrodes with high capacity, high rate capability, and excellent cycling stability. PMID:26646734

  5. Generation of solution plasma over a large electrode surface area

    NASA Astrophysics Data System (ADS)

    Saito, Genki; Nakasugi, Yuki; Akiyama, Tomohiro

    2015-07-01

    Solution plasma has been used in a variety of fields such as nanomaterials synthesis, the degradation of harmful substances, and solution analysis. However, as existing methods are ineffective in generating plasma over a large surface area, this study investigated the contact glow discharge electrolysis, in which the plasma was generated on the electrode surface. To clarify the condition of plasma generation, the effect of electrolyte concentration and temperature on plasma formation was studied. The electrical energy needed for plasma generation is higher than that needed to sustain a plasma, and when the electrolyte temperature was increased from 32 to 90 °C at 0.01 M NaOH solution, the electric power density for vapor formation decreased from 2005 to 774 W/cm2. From these results, we determined that pre-warming of the electrolyte is quite effective in generating plasma at lower power density. In addition, lower electrolyte concentrations required higher power density for vapor formation owing to lower solution conductivity. On the basis these results, a method for large-area and flat-plate plasma generation is proposed in which an initial small area of plasma generation is extended. When used with a plate electrode, a concentration of current to the edge of the plate meant that plasma could be formed by covering the edge of the electrode plate.

  6. Effect of multipactor conditioning on technical electrode surfaces

    SciTech Connect

    Graves, T. P.; Spektor, R.; Stout, P.

    2009-11-26

    Historically, multipactor conditioning has been utilized to remove surface contaminants from rf electrodes by electron-stimulated gas desorption, and such conditioning has been shown to reduce multipactor susceptibility. Multipactor threshold improvements are due to increasing E{sub 1}, the minimum energy for the secondary electron coefficient, {delta}>1, such that resonant electrons are incapable of producing discharge-sustaining secondary emission. Using an rf amplitude sweep technique, the evolution of the multipactor threshold is measured as a function of multipactor conditioning time for a series of technical electrode surfaces. Results show over +3 dB of threshold improvement in copper and gold electrodes, while the aluminum threshold actually decreases with conditioning exposure. Additionally, these conditioning results indicate the possible voltage region for transient-mode multipaction (TMM), which can cause significant risk to rf systems such as space satellite components for which in-situ conditioning is generally not possible. Experimental results and supporting Monte Carlo particle tracking simulation results are presented.

  7. Lithium intercalation and structural changes at the LiCoO2 surface under high voltage battery operation

    NASA Astrophysics Data System (ADS)

    Taminato, Sou; Hirayama, Masaaki; Suzuki, Kota; Tamura, Kazuhisa; Minato, Taketoshi; Arai, Hajime; Uchimoto, Yoshiharu; Ogumi, Zempachi; Kanno, Ryoji

    2016-03-01

    An epitaxial-film model electrode of LiCoO2(104) was fabricated on SrRuO3(100)/Nb:SrTiO3(100) using pulsed laser deposition. The 50 nm thick LiCoO2(104) film exhibited lithium (de-)intercalation activity with a first discharge capacity of 119 mAh g-1 between 3.0 and 4.4 V, followed by a gradual capacity fading with subsequent charge-discharge cycles. In contrast, a 3.2 nm thick Li3PO4-coated film exhibited a higher intercalation capacity of 148 mAh g-1 with superior cycle retention than the uncoated film. In situ surface X-ray diffraction measurements revealed a small lattice change at the coated surface during the (de-)intercalation processes compared to the uncoated surface. The surface modification of LiCoO2 by the Li3PO4 coating could lead to improvement of the structural stability at the surface region during lithium (de-)intercalation at high voltage.

  8. Mesoporous Li4Ti5O12 nanoclusters anchored on super-aligned carbon nanotubes as high performance electrodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sun, Li; Kong, Weibang; Wu, Hengcai; Wu, Yang; Wang, Datao; Zhao, Fei; Jiang, Kaili; Li, Qunqing; Wang, Jiaping; Fan, Shoushan

    2015-12-01

    Mesoporous lithium titanate (LTO) nanoclusters are in situ synthesized in a network of super aligned carbon nanotubes (SACNTs) via a solution-based method followed by heat treatment in air. In the LTO-CNT composite, SACNTs not only serve as the skeleton to support a binder-free electrode, but also render the composite with high conductivity, flexibility, and mechanical strength. The homogeneously dispersed LTO nanoclusters among the SACNTs allow each LTO grain to effectively access the electrolyte and the conductive network, benefiting both ion and electron transport. By the incorporation of LTO into the CNT network, mechanical reinforcement is also achieved. When serving as a negative electrode for lithium ion batteries, such a robust composite-network architecture provides the electrodes with effective charge transport and structural integrity, leading to high-performance flexible electrodes with high capacity, high rate capability, and excellent cycling stability.Mesoporous lithium titanate (LTO) nanoclusters are in situ synthesized in a network of super aligned carbon nanotubes (SACNTs) via a solution-based method followed by heat treatment in air. In the LTO-CNT composite, SACNTs not only serve as the skeleton to support a binder-free electrode, but also render the composite with high conductivity, flexibility, and mechanical strength. The homogeneously dispersed LTO nanoclusters among the SACNTs allow each LTO grain to effectively access the electrolyte and the conductive network, benefiting both ion and electron transport. By the incorporation of LTO into the CNT network, mechanical reinforcement is also achieved. When serving as a negative electrode for lithium ion batteries, such a robust composite-network architecture provides the electrodes with effective charge transport and structural integrity, leading to high-performance flexible electrodes with high capacity, high rate capability, and excellent cycling stability. Electronic supplementary information

  9. Doping level influence on chemical surface of diamond electrodes

    NASA Astrophysics Data System (ADS)

    Azevedo, A. F.; Baldan, M. R.; Ferreira, N. G.

    2013-04-01

    The modification of surface bond termination promoted by the doping level on diamond electrodes is analyzed. The films were prepared by hot filament chemical vapor deposition technique using the standard mixture of H2/CH4 with an extra H2 flux passing through a bubbler containing different concentrations of B2O3 dissolved in methanol. Diamond morphology and quality were characterized by scanning electron microscopy and Raman scattering spectroscopy techniques while the changes in film surfaces were analyzed by contact angle, cyclic voltammetry and synchrotron X-ray photoelectron spectroscopy (XPS). The boron-doped diamond (BDD) films hydrophobicity, reversibility, and work potential window characteristics were related to their physical properties and chemical surface, as a function of the doping level. From the Mott-Schottky plots (MSP) and XPS analyzes, for the lightly (1018 cm-3) and highly (1020 cm-3) BDD films, the relationship between the BDD electrochemical responses and their surface bond terminations is discussed.

  10. Lithium

    MedlinePlus

    ... mania (frenzied, abnormally excited mood) in people with bipolar disorder (manic-depressive disorder; a disease that causes episodes of depression, episodes of mania, and other abnormal moods). Lithium is in a ... antimanic agents. It works by decreasing abnormal activity in the brain.

  11. Mars Mission Surface Operation Simulation Testing of Lithium-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Bugga, R.; Whitcanack, L. D.; Chin, K. B.; Davies, E. D.; Surampudi, S.

    2003-01-01

    The objectives of this program are to 1) Assess viability of using lithium-ion technology for future NASA applications, with emphasis upon Mars landers and rovers which will operate on the planetary surface; 2) Support the JPL 2003 Mars Exploration Rover program to assist in the delivery and testing of a 8 AHr Lithium-Ion battery (Lithion/Yardney) which will power the rover; 3) Demonstrate applicability of using lithium-ion technologyfor future Mars applications: Mars 09 Science Laboratory (Smart Lander) and Future Mars Surface Operations (General). Mission simulation testing was carried out for cells and batteries on the Mars Surveyor 2001 Lander and the 2003 Mars Exploration Rover.

  12. Structure and surface chemistry of Al2O3 coated LiMn2O4 nanostructured electrodes with improved lifetime

    NASA Astrophysics Data System (ADS)

    Waller, G. H.; Brooke, P. D.; Rainwater, B. H.; Lai, S. Y.; Hu, R.; Ding, Y.; Alamgir, F. M.; Sandhage, K. H.; Liu, M. L.

    2016-02-01

    Aluminum oxide coatings deposited on LiMn2O4/carbon fiber electrodes by atomic layer deposition (ALD) are shown to enhance cathode performance in lithium-ion batteries. With a thin Al2O3 coating derived from 10 ALD cycles, the electrodes exhibit 2.5 times greater capacity retention over 500 cycles at a rate of 1C as well as enhanced rate capability and decreased polarization resistance. Structural and surface studies of the electrodes before and after cycling reveal that a near-surface phenomenon is responsible for the improved electrochemical performance. The crystal structure and overall morphology of the LiMn2O4 electrode are found to be unaffected by electrochemical cycling, both for coated and uncoated samples. However, evidence of Mn diffusion into the ALD coatings is observed from both transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM-EDS) and X-ray Photoelectron Spectroscopy (XPS) after electrochemical cycling. Furthermore, XPS analysis of the Al 2p photoemission peak for the ALD coated electrodes reveal a significant shift in binding energy and peak shape, suggesting the presence of an Al-O-F compound formed by sequestering HF in the electrolyte. These observations provide new insight toward understanding the mechanism in which ultrathin coatings of amphoteric oxides can inhibit capacity loss for LiMn2O4 cathodes in lithium-ion batteries.

  13. Development and In Situ Characterization of New Electrolyte and Electrode materials for Rechargeable Lithium Batteries

    SciTech Connect

    Yang, X -Q; Xing, X K; Daroux, M

    2000-01-03

    The object of this project is to develop new electrolyte and cathode materials for rechargeable lithium batteries, especially for lithium ion and lithium polymer batteries. Enhancing performance, reducing cost, and replacing toxic materials by environmentally benign materials, are strategic goals of DOE in lithium battery research. This proposed project will address these goals on two important material studies, namely the new electrolytes and new cathode materials. For the new electrolyte materials, aza based anion receptors as additives, organic lithium salts and plasticizers which have been developed by BNL team under Energy Research programs of DOE, will be evaluated by Gould for potential use in commercial battery cells. All of these three types of compounds are aimed to enhance the conductivity and lithium transference number of lithium battery electrolytes and reduce the use of toxic salts in these electrolytes. BNL group will be working closely with Gould to further develop these compounds for commercialization. For the cathode material studies, BNL efforts wi U be focused on developing new superior characterization methclds, especially in situ techniques utilize the unique user facility of DOE at BNL, namely the National Synchrotrons Light Source (NSLS). In situ x-ray absorption and x-ray diftlaction spectroscopy will be used to study the relationship between performance and the electronic and structural characteristics of intercalation compounds such as LiNi02, LiCo02, and LiMn204 spinel. The study will be focused on LiMn204 spinel materials. Gould team will contribute their expertise in choosing the most promising compounds, providing overall performance requirements, and will use the results of this study to guide their procedure for quality control. The knowledge gained through this project will not only benefit Gould and BNL, but will be very valuable to the scientific community in

  14. Revisiting Surface Modification of Graphite: Dual-Layer Coating for High-Performance Lithium Battery Anode Materials.

    PubMed

    Song, Gyujin; Ryu, Jaegeon; Ko, Seunghee; Bang, Byoung Man; Choi, Sinho; Shin, Myoungsoo; Lee, Sang-Young; Park, Soojin

    2016-06-01

    Surface modification of electrode active materials has garnered considerable attention as a facile way to meet stringent requirements of advanced lithium-ion batteries. Here, we demonstrated a new coating strategy based on dual layers comprising antimony-doped tin oxide (ATO) nanoparticles and carbon. The ATO nanoparticles are synthesized via a hydrothermal method and act as electronically conductive/electrochemically active materials. The as-synthesized ATO nanoparticles are introduced on natural graphite along with citric acid used as a carbon precursor. After carbonization, the carbon/ATO-decorated natural graphite (c/ATO-NG) is produced. In the (carbon/ATO) dual-layer coating, the ATO nanoparticles coupled with the carbon layer exhibit unprecedented synergistic effects. The resultant c/ATO-NG anode materials display significant improvements in capacity (530 mA h g(-1) ), cycling retention (capacity retention of 98.1 % after 50 cycles at a rate of C/5), and low electrode swelling (volume expansion of 38 % after 100 cycles) which outperform that of typical graphite materials. Furthermore, a full-cell consisting of a c/ATO-NG anode and an LiNi0.5 Mn1.5 O4 cathode presents excellent cycle retention (capacity retention of >80 % after 100 cycles). We envision that the dual-layer coating concept proposed herein opens a new route toward high-performance anode materials for lithium-ion batteries. PMID:27027583

  15. Ab initio study of radiation effects on the Li4Ti5O12 electrode used in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Samin, Adib; Kurth, Michael; Cao, Lei

    2015-04-01

    Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li4Ti5O12 is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced.

  16. Ab initio study of radiation effects on the Li{sub 4}Ti{sub 5}O{sub 12} electrode used in lithium-ion batteries

    SciTech Connect

    Samin, Adib E-mail: cao.152@osu.edu; Kurth, Michael; Cao, Lei E-mail: cao.152@osu.edu

    2015-04-15

    Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li{sub 4}Ti{sub 5}O{sub 12} is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced.

  17. Experimental demonstration of a surface-electrode multipole ion trap

    NASA Astrophysics Data System (ADS)

    Maurice, Mark; Allen, Curtis; Green, Dylan; Farr, Andrew; Burke, Timothy; Hilleke, Russell; Clark, Robert

    2015-08-01

    We report on the design and experimental characterization of a surface-electrode multipole ion trap. Individual microscopic sugar particles are confined in the trap. The trajectories of driven particle motion are compared with a theoretical model, both to verify qualitative predictions of the model and to measure the charge-to-mass ratio of the confined particle. The generation of harmonics of the driving frequency is observed as a key signature of the nonlinear nature of the trap. We remark on possible applications of our traps, including to mass spectrometry.

  18. Discontinuous and Continuous Processing of Low-Solvent Battery Slurries for Lithium Nickel Cobalt Manganese Oxide Electrodes

    NASA Astrophysics Data System (ADS)

    Dreger, Henning; Bockholt, Henrike; Haselrieder, Wolfgang; Kwade, Arno

    2015-11-01

    Different discontinuously and continuously working dispersing devices were investigated to determine their influence on the structural and electrochemical properties of electrodes made from commercial LiNi1/3Co1/3Mn1/3O2 (NCM) cathode active material. A laboratory-scale dispersing device was compared with a discontinuously working laboratory kneader and a continuously working extruder, both using 50% less solvent than the dissolver process. Rheological, mechanical, structural, conductive, imaging, and electrochemical analyses (C-rate test, long-term cycling) were carried out. The dispersing method and time were found to have a considerable impact on the structure and electrochemical performance. The continuous extrusion process resulted in good performance with more than 20% higher specific capacity at elevated C-rates compared with the discontinuous process. This can be attributed to better deagglomeration of the carbon black in the slurries, also resulting in 60% higher electrode conductivity. On top of these positive results, the changes in the drying step due to the reduced solvent use led to a 50% decrease in the time required for the constant-drying-rate period. The continuously working extrusion process was found to be most suitable for large-scale, cost-efficient, environmentally friendly production of slurries for lithium-ion battery electrodes.

  19. A review of thermal performance improving methods of lithium ion battery: Electrode modification and thermal management system

    NASA Astrophysics Data System (ADS)

    Zhao, Rui; Zhang, Sijie; Liu, Jie; Gu, Junjie

    2015-12-01

    Lithium ion (Li-ion) battery has emerged as an important power source for portable devices and electric vehicles due to its superiority over other energy storage technologies. A mild temperature variation as well as a proper operating temperature range are essential for a Li-ion battery to perform soundly and have a long service life. In this review paper, the heat generation and dissipation of Li-ion battery are firstly analyzed based on the energy conservation equations, followed by an examination of the hazardous effects of an above normal operating temperature. Then, advanced techniques in respect of electrode modification and systematic battery thermal management are inspected in detail as solutions in terms of reducing internal heat production and accelerating external heat dissipation, respectively. Specifically, variable parameters like electrode thickness and particle size of active material, along with optimization methods such as coating, doping, and adding conductive media are discussed in the electrode modification section, while the current development in air cooling, liquid cooling, heat pipe cooling, and phase change material cooling systems are reviewed in the thermal management part as different ways to improve the thermal performance of Li-ion batteries.

  20. Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

    DOEpatents

    Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuliang; Li, Xiaolin

    2015-04-07

    A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

  1. The structural and electrochemical dynamics of the electrode-electrolyte interphase of metal fluoride nanocomposite positive electrodes for lithium batteries

    NASA Astrophysics Data System (ADS)

    Gmitter, Andrew John

    Metal fluorides are attractive for use as positive electrodes in Li and Li-ion batteries because of their high gravimetric and volumetric energy densities. When synthesized into nanocomposites, these materials undergo conversion reactions and exhibit near theoretical specific capacity and good rate capability. Despite these positive attributes, metal fluorides nanocomposites generally exhibit unacceptable rates of capacity loss during cycling. This stands as a significant barrier to their realization as a viable battery technology. This thesis explored a candidate material, BiF3, and for the first time, the mechanisms by which metal fluoride nanocomposite positive electrode materials fail during cycling have been investigated. The chemistry of the electrode / electrolyte interface and its influence on the BiF3 material were of greatest interest. Early in the course of study, it was discovered that the Bi0 metal produced through the discharge reaction of BiF3 was a catalytically active site for the electrochemical reduction of ethylene carbonate (EC) at potentials exceeding 2 V vs. Li/Li+. This potential range is well above the values typically observed on carbonaceous negative electrodes on which preferential reduction of electrolyte species yields insoluble phases. These ionically conducting layers are deemed solid-electrolyte interphases (SEI), and in the case of carbonaceous materials, they are necessary for enabling functionality of the electrode and preventing deleterious interactions with the electrolyte. Thorough electrochemical and spectroscopic examinations identified Li2CO3 as the predominant SEI species formed on Bi0 from EC. In stark contrast to carbonaceous materials, the presence of SEI on Bi0 was detrimental to the cycling performance of BiF3. Elaboration of this topic identified instability of the SEI during the charging process of the BiF3 and the formation of BiOxF3-2x in the fully charged state. Electrolytes composed of linear

  2. SnO{sub 2}/ZnO composite structure for the lithium-ion battery electrode

    SciTech Connect

    Ahmad, Mashkoor; Yingying, Shi; Sun, Hongyu; Shen, Wanci; Zhu, Jing

    2012-12-15

    In this article, SnO{sub 2}/ZnO composite structures have been synthesized by two steps hydrothermal method and investigated their lithium storage capacity as compared with pure ZnO. It has been found that these composite structures combining the large specific surface area, stability and catalytic activity of SnO{sub 2} micro-crystals, demonstrate the higher initial discharge capacity of 1540 mA h g{sup -1} with a Coulombic efficiency of 68% at a rate of 120 mA h g{sup -1} between 0.02 and 2 V and found much better than that of any previously reported ZnO based composite anodes. In addition, a significantly enhanced cycling performance, i.e., a reversible capacity of 497 mA h g{sup -1} is retained after 40 cycles. The improved lithium storage capacity and cycle life is attributed to the addition of SnO{sub 2} structure, which act as good electronic conductors and better accommodation of the large volume change during lithiation/delithiation process. - Graphical abstract: SnO{sub 2}/ZnO composite structures demonstrate the improved lithium storage capacity and cycle life as compared with pure ZnO nanostructure. Highlights: Black-Right-Pointing-Pointer Synthesis of SnO{sub 2}/ZnO composite structures by two steps hydrothermal approach. Black-Right-Pointing-Pointer Investigation of lithium storage capacity. Black-Right-Pointing-Pointer Excellent lithium storage capacity and cycle life of SnO{sub 2}/ZnO composite structures.

  3. High-strength clad current collector for silicon-based negative electrode in lithium ion battery

    NASA Astrophysics Data System (ADS)

    Kataoka, Riki; Oda, Yoshimitsu; Inoue, Ryouji; Kitta, Mitsunori; Kiyobayashi, Tetsu

    2016-01-01

    We develop a clad foil current collector with a high tensile strength that endures a large volume change in the active material during the charge and discharge, such as the Si-based materials. The nano-Si negative electrode with the clad current collector retains 76% of the initial capacity after 40 cycles, while the capacity of the nano-Si electrode with a conventional Cu foil drops to less than 70% only after 10 cycles. A full cell with the SiO negative electrode and the LiFePO4 positive electrode retains more than 90% of its capacity at the 10th cycle after 800 cycles. The conventional rolled Cu foil wrinkles during the cycling test. The high-strength clad current foil hardly deforms during the test regardless of the electrode size.

  4. Photoinduced surface dynamics of CO adsorbed on a platinum electrode.

    PubMed

    Noguchi, Hidenori; Okada, Tsubasa; Uosaki, Kohei

    2006-08-10

    The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation. PMID:16884215

  5. Surface Studies of High Voltage Lithium Rich Composition: Li1.2Mn0.525Ni0.175Co0.1O2

    SciTech Connect

    Martha, Surendra K; Veith, Gabriel M; Dudney, Nancy J; Nanda, Jagjit

    2012-01-01

    This article reports the evidence of surface film formation because of the breakdown of electrolyte upon high voltage cycling (4.9 V) of lithium rich cathode having a nominal composition of, Li1.2Mn0.525Ni0.175Co0.1O2. We studied the chemical composition of this passivation film using electrochemical impedance, X-ray Photoelectron and micro-Raman spectroscopy and the results were compared against the pristine electrode. In order to distinguish the changes in the surface films composition induced by prolonged electrochemical cycling versus chemical passivation effect, we also studied the surface composition of cathode powders aged with electrolytes at 60 oC. Our study shows that electrodes cycled beyond 150 cycles showed a rapid drop in capacity due to increase in the surface film resistance resulting in limited capacity utilization.

  6. Surface complex formation between aliphatic nitrile molecules and transition metal atoms for thermally stable lithium-ion batteries.

    PubMed

    Kim, Young-Soo; Lee, Hochun; Song, Hyun-Kon

    2014-06-11

    Non-flammability of electrolyte and tolerance of cells against thermal abuse should be guaranteed for widespread applications of lithium-ion batteries (LIBs). As a strategy to improve thermal stability of LIBs, here, we report on nitrile-based molecular coverage on surface of cathode active materials to block or suppress thermally accelerated side reactions between electrode and electrolyte. Two different series of aliphatic nitriles were introduced as an additive into a carbonate-based electrolyte: di-nitriles (CN-[CH2]n-CN with n = 2, 5, and 10) and mono-nitriles (CH3-[CH2]m-CN with m = 2, 5, and 10). On the basis of the strong interaction between the electronegativity of nitrile functional groups and the electropositivity of cobalt in LiCoO2 cathode, aliphatic mono- and di-nitrile molecules improved the thermal stability of lithium ion cells by efficiently protecting the surface of LiCoO2. Three factors, the surface coverage θ, the steric hindrance of aliphatic moiety within nitrile molecule, and the chain polarity, mainly affect thermal tolerance as well as cell performances at elevated temperature. PMID:24836760

  7. Sulfur Embedded in a Mesoporous Carbon Nanotube Network as a Binder-Free Electrode for High-Performance Lithium-Sulfur Batteries.

    PubMed

    Sun, Li; Wang, Datao; Luo, Yufeng; Wang, Ke; Kong, Weibang; Wu, Yang; Zhang, Lina; Jiang, Kaili; Li, Qunqing; Zhang, Yihe; Wang, Jiaping; Fan, Shoushan

    2016-01-26

    Sulfur-porous carbon nanotube (S-PCNT) composites are proposed as cathode materials for advanced lithium-sulfur (Li-S) batteries. Abundant mesopores are introduced to superaligned carbon nanotubes (SACNTs) through controlled oxidation in air to obtain porous carbon nanotubes (PCNTs). Compared to original SACNTs, improved dispersive behavior, enhanced conductivity, and higher mechanical strength are demonstrated in PCNTs. Meanwhile, high flexibility and sufficient intertube interaction are preserved in PCNTs to support binder-free and flexible electrodes. Additionally, several attractive features, including high surface area and abundant adsorption points on tubes, are introduced, which allow high sulfur loading, provide dual protection to sulfur cathode materials, and consequently alleviate the capacity fade especially during slow charge/discharge processes. When used as cathodes for Li-S batteries, a high sulfur loading of 60 wt % is achieved, with excellent reversible capacities of 866 and 526 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at a slow charge/discharge rate of 0.1C, revealing efficient suppression of polysulfide dissolution. Even with a high sulfur loading of 70 wt %, the S-PCNT composite maintains capacities of 760 and 528 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at 0.1C, outperforming the current state-of-the-art sulfur cathodes. Improved high-rate capability is also delivered by the S-PCNT composites, revealing their potentials as high-performance carbon-sulfur composite cathodes for Li-S batteries. PMID:26695394

  8. Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

    DOEpatents

    Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

    2014-06-17

    Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

  9. Electrochemical study of Si/C composites with particulate and fibrous morphology as negative electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gómez-Cámer, Juan Luis; Thuv, Heidi; Novák, Petr

    2015-10-01

    Silicon-carbon composites with two different morphologies, particulate and fibrous, prepared by NaOH catalyzed polymerization of resorcinol and formaldehyde in presence of Si nanoparticles and cosurfactants, are examined as negative electrodes in lithium-ion batteries. The composites prepared with ca. 33, 50, and 66% Si deliver around 1000, 1500, and 2000 mAh g-1, respectively. Higher silicon content results in higher initial specific charge, but also faster fading during cycling. The composites with the lowest silicon content exhibit the most stable specific charges. The differences in electrochemical behavior for the optimized compositions are investigated by means of microscopy and electrochemical impedance analysis and are discussed in terms of morphology of the different composites.

  10. Fabricating solid carbon porous electrodes from powders

    DOEpatents

    Kaschmitter, James L.; Tran, Tri D.; Feikert, John H.; Mayer, Steven T.

    1997-01-01

    Fabrication of conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive dionization, and waste treatment. Electrodes fabricated from low surface area (<50 m.sup.2 /gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon compositives with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to be high surface area carbons, fuel cell electrodes can be produced.

  11. Fabricating solid carbon porous electrodes from powders

    DOEpatents

    Kaschmitter, J.L.; Tran, T.D.; Feikert, J.H.; Mayer, S.T.

    1997-06-10

    Fabrication is described for conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive deionization, and waste treatment. Electrodes fabricated from low surface area (<50 m{sup 2}/gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon composites with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to high surface area carbons, fuel cell electrodes can be produced. 1 fig.

  12. Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean M.; Palker, Allyson E.; Meador, Mary Ann B.; Bennett, William R.

    2008-01-01

    A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

  13. Lithium plating in a commercial lithium-ion battery - A low-temperature aging study

    NASA Astrophysics Data System (ADS)

    Petzl, Mathias; Kasper, Michael; Danzer, Michael A.

    2015-02-01

    The formation of metallic lithium on the negative graphite electrode in a lithium-ion (Li-ion) battery, also known as lithium plating, leads to severe performance degradation and may also affect the cell safety. This study is focused on the nondestructive characterization of the aging behavior during long-term cycling at plating conditions, i.e. low temperature and high charge rate. A commercial graphite/LiFePO4 Li-ion battery is investigated in order to elucidate the aging effects of lithium plating for real-world purposes. It is shown that lithium plating can be observed as a loss of cyclable lithium which affects the capacity balance of the electrodes. In this way, lithium plating counteracts its own occurrence during prolonged cycling. The capacity losses due to lithium plating are therefore decreasing at higher cycle numbers and the capacity retention curve exhibits an inflection point. It is further shown that the observed capacity fade is partly reversible. Electrochemical impedance spectroscopy (EIS) reveals a significant increase of the ohmic cell resistance due to electrolyte consumption during surface film formation on the plated lithium. Additional cell opening provides important quantitative information regarding the thickness of the lithium layer and the corresponding mass of the plated lithium.

  14. Surface reactivity of graphite materials and their surface passivation during the first electrochemical lithium insertion

    NASA Astrophysics Data System (ADS)

    Spahr, Michael E.; Buqa, Hilmi; Würsig, Andreas; Goers, Dietrich; Hardwick, Laurence; Novák, Petr; Krumeich, Frank; Dentzer, Joseph; Vix-Guterl, Cathie

    The surface passivation of TIMREX ® SLX50 graphite powder was studied as received and after heat treatment at 2500 °C in an inert gas atmosphere by differential electrochemical mass spectrometry in electrochemical lithium half-cells. 1 M LiPF 6 in ethylene carbonate and either a dimethyl carbonate, propylene carbonate or 1-fluoro ethylene carbonate co-solvent was used as electrolyte systems in these half-cells. The SEI-film formation properties of both graphite materials were correlated with their active surface area (ASA), being responsible for the interactions between the carbon and the electrolyte system. The active surface area was determined from the amount of CO and CO 2 gas desorbed at temperatures up to 950 °C from the graphite material surface after chemisorption of oxygen at 300 °C. The structural ordering at the graphite surface increased significantly during the heat treatment of the SLX50 graphite material as indicated by the significant decrease of the ASA value. The increased surface crystallinity was confirmed by krypton gas adsorption, Raman spectroscopy as well as temperature-programmed desorption. This increased structural ordering seemed to be the parameter being responsible for a hindered passivation of the heat-treated SLX50 causing partial exfoliation of the graphite structure during the first electrochemical lithium insertion in the ethylene carbonate/dimethyl carbonate electrolyte. In the case of the ethylene carbonate/1-fluoro ethylene carbonate electrolyte system, primarily the fluoro compound is responsible for the graphite passivation. In this electrolyte system, pristine SLX50 and the less reactive, heat-treated SLX50 graphite showed significantly different SEI-film formation mechanisms. In contrast, no difference in the passivation mechanism could be identified for different graphite surfaces in the ethylene carbonate electrolyte system with propylene carbonate as co-solvent.

  15. Composite polymer positive electrodes in solid-state lithium secondary batteries

    SciTech Connect

    Novak, P.; Inganas, O.; Bjorklund, R.

    1987-06-01

    The authors have developed composite polymer electrodes for use in all solid-state batteries in combination with Li. The composite is formed from water soluble polypyrrole which is combined with the solid polymer electrolyte polyethylene oxide. The composite electrode shows enhanced coulombic capacity as compared to an electrode composed only of the electroactive material, polypyrrole. Coulombic efficiency is good (90-95%) and energy efficiency is acceptable (80-85%) in galvanostatic studies. Charge retention is rather poor due to self-discharge. They have obtained proof that the electroactivity is due to polypyrrole, through the use of in situ spectroelectrochemical studies. They have characterized the composite electrode using scanning electron microscopy and conductive measurements.

  16. A system for performing simultaneous in situ atomic force microscopy/optical microscopy measurements on electrode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Beaulieu, L. Y.; Cumyn, V. K.; Eberman, K. W.; Krause, L. J.; Dahn, J. R.

    2001-08-01

    An atomic force microscope (AFM) equipped with an optical charge coupled device camera has been placed in an Ar filled glovebox for the purpose of studying the change in morphology of electrode materials as they react with lithium. In order to minimize noise induced by vibration, the AFM is mounted on granite blocks suspended from the ceiling of the glovebox by a combination of flexible rubber cords and metal springs. The AFM, which is equipped with an environmental chamber surrounding the sample, is then enclosed in a specially constructed draft shield that allows the circulation of Ar gas by the purification system during imaging. A special electrochemical cell was constructed to hold the working electrode under study. Repeated imaging with little drift is possible while electrodes are reacted with lithium for periods of many days. Examples of measurements made by this device will be given for the case of lithium alloying with sputter-deposited Si-Sn thin films. The optical and AFM images obtained as a function of lithium content in the films are assembled into time-lapsed "movies" showing the evolution of the morphology of the sample along with the corresponding electrochemistry. These movies are available for download through the Electronic Physics Auxiliary Publication Service (EPAPS).

  17. Continuity and Performance in Composite Electrodes

    SciTech Connect

    Chen, Guoying; Richardson, Thomas J.

    2009-12-23

    It is shown that the rate performance of a lithium battery composite electrode may be compromised by poor internal connectivity due to defects and inhomogeneities introduced during electrode fabrication or subsequent handling. Application of a thin conductive coating to the top surface of the electrode or to the separator surface in contact with the electrode improves the performance by providing alternative current paths to partially isolated particles of electroactive material. Mechanistic implications are discussed and strategies for improvement in electrode design and fabrication are presented.

  18. X-ray absorption spectroscopic study of LiCoO2 as the negative electrode of lithium-ion batteries.

    PubMed

    Chadwick, Alan V; Savin, Shelley L P; Alcántara, Ricardo; Fernández Lisbona, Diego; Lavela, Pedro; Ortiz, Gregorio F; Tirado, José L

    2006-05-12

    Lithium cobalt oxide (LiCoO(2)) particles are modified using rotor blade grinding and re-annealing and used as the active electrode material versus lithium in the 3-0 V potential interval, in which a maximum capacity of 903 mA h g(-1) is achieved. X-ray absorption near edge structure spectra reveal the complete reduction of Co(3+) to Co metal at 0 V. Cell recharge leads to an incomplete reoxidation of cobalt. A maximum reversible capacity of 812 mA h g(-1) is obtained, although a poor capacity retention upon prolonged cycling may limit its application. PMID:16612798

  19. Material Surface Characteristics and Plasma Performance in the Lithium Tokamak Experiment

    NASA Astrophysics Data System (ADS)

    Lucia, Matthew James

    The performance of a tokamak plasma and the characteristics of the surrounding plasma facing component (PFC) material surfaces strongly influence each other. Despite this relationship, tokamak plasma physics has historically been studied more thoroughly than PFC surface physics. The disparity is particularly evident in lithium PFC research: decades of experiments have examined the effect of lithium PFCs on plasma performance, but the understanding of the lithium surface itself is much less complete. This latter information is critical to identifying the mechanisms by which lithium PFCs affect plasma performance. This research focused on such plasma-surface interactions in the Lithium Tokamak Experiment (LTX), a spherical torus designed to accommodate solid or liquid lithium as the primary PFC. Surface analysis was accomplished via the novel Materials Analysis and Particle Probe (MAPP) diagnostic system. In a series of experiments on LTX, the MAPP x-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS) capabilities were used for in vacuo interrogation of PFC samples. This represented the first application of XPS and TDS for in situ surface analysis of tokamak PFCs. Surface analysis indicated that the thin (dLi ˜ 100nm) evaporative lithium PFC coatings in LTX were converted to Li2O due to oxidizing agents in both the residual vacuum and the PFC substrate. Conversion was rapid and nearly independent of PFC temperature, forming a majority Li2O surface within minutes and an entirely Li2O surface within hours. However, Li2O PFCs were still capable of retaining hydrogen and sequestering impurities until the Li2 O was further oxidized to LiOH, a process that took weeks. For hydrogen retention, Li2O PFCs retained H+ from LTX plasma discharges, but no LiH formation was observed. Instead, results implied that H+ was only weakly-bound, such that it almost completely outgassed as H 2 within minutes. For impurity sequestration, LTX plasma performance

  20. Laser ablation loading of a surface-electrode ion trap

    SciTech Connect

    Leibrandt, David R.; Clark, Robert J.; Labaziewicz, Jaroslaw; Antohi, Paul; Bakr, Waseem; Brown, Kenneth R.; Chuang, Isaac L.

    2007-11-15

    We demonstrate loading of {sup 88}Sr{sup +} ions by laser ablation into a mm-scale surface-electrode ion trap. The laser used for ablation is a pulsed, frequency-tripled Nd:YAG with pulse energies of 1-10 mJ and durations of 4 ns. An additional laser is not required to photoionize the ablated material. The efficiency and lifetime of several candidate materials for the laser ablation target are characterized by measuring the trapped ion fluorescence signal for a number of consecutive loads. Additionally, laser ablation is used to load traps with a trap depth (40 meV) below where electron impact ionization loading is typically successful (> or approx. 500 meV)

  1. Modified carbon-free silver electrodes for the use as cathodes in lithium-air batteries with an aqueous alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Wittmaier, Dennis; Wagner, Norbert; Friedrich, K. Andreas; Amin, Hatem M. A.; Baltruschat, Helmut

    2014-11-01

    Gas diffusion electrodes with silver catalysts show a high activity towards oxygen reduction reaction in alkaline media but a rather poor activity towards oxygen evolution reaction. For the use in future lithium-air batteries with an aqueous alkaline electrolyte the activity of such electrodes must be improved significantly. As Co3O4 is a promising metal oxide catalyst for oxygen evolution in alkaline media, silver electrodes were modified with Co3O4. For comparison silver electrodes were also modified with IrO2. Due to the poor stability of carbon materials at high anodic potentials these gas diffusion electrodes were prepared without carbon support to improve especially the long-term stability. Gas diffusion electrodes were electrochemically investigated in an electrochemical half-cell arrangement. In addition to cyclic voltammograms electrochemical impedance spectroscopy (EIS) was carried out. SEM and XRD were used for the physical and morphological investigations. Investigations showed that silver electrodes containing 20 wt.% Co3O4 exhibited the highest performance and highest long-term stability. For comparison, rotating - ring - disc - electrode experiments have been performed using model electrodes with thin catalyst layers, showing that the amount of hydrogen peroxide evolved is negligible.

  2. Water soluble styrene butadiene rubber and sodium carboxyl methyl cellulose binder for ZnFe2O4 anode electrodes in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Rongyu; Yang, Xu; Zhang, Dong; Qiu, Hailong; Fu, Qiang; Na, Hui; Guo, Zhendong; Du, Fei; Chen, Gang; Wei, Yingjin

    2015-07-01

    ZnFe2O4 nano particles as an anode material for lithium ion batteries are prepared by the glycine-nitrate combustion method. The mixture of styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC) with the weight ratio of 1:1 is used as the binder for ZnFe2O4 electrode. Compared with the conventional polyvinylidene-fluoride (PVDF) binder, the SBR/CMC binder is much cheaper and environment benign. More significantly, this water soluble binder significantly improves the rate capability and cycle stability of ZnFe2O4. A discharge capacity of 873.8 mAh g-1 is obtained after 100 cycles at the 0.1C rate, with a very little capacity fading rate of 0.06% per cycle. Studies show that the SBR/CMC binder enhances the adhesion of the electrode film to the current collector, and constructs an effective three-dimensional network for electrons transport. In addition, the SBR/CMC binder helps to form a uniform SEI film thus prohibiting the formation of lithium dendrite. Electrochemical impedance spectroscopy shows that the SBR/CMC binder lowers the ohmic resistance of the electrode, depresses the formation of SEI film and facilitates the charge transfer reactions at the electrode/electrolyte interface. These advantages highlight the potential applications of SBR/CMC binder in lithium ion batteries.

  3. Computational, electrochemical and {sup 7}Li NMR studies of lithiated disordered carbons electrodes in lithium ion cells.

    SciTech Connect

    Sandi, G.; Gerald, R., II; Scanlon, L. G.; Carrado, K. A.; Winans, R. E.

    1998-01-07

    Disordered carbons that deliver high reversible capacity in electrochemical cells have been synthesized by using inorganic clays as templates to control the pore size and the surface area. The capacities obtained were much higher than those calculated if the resultant carbon had a graphitic-like structure. Computational chemistry was used to investigate the nature of lithium bonding in a carbon lattice unlike graphite. The lithium intercalated fullerene Li{sub n}-C{sub 60} was used as a model for our (non-graphitic) disordered carbon lattice. A dilithium-C{sub 60} system with a charge and multiplicity of (0,1) and a trilithium-C{sub 60} system with a charge and multiplicity of (0,4) were investigated. The spatial distribution of lithium ions in an electrochemical cell containing this novel disordered carbon material was investigated in situ by Li-7 NMR using an electrochemical cell that was incorporated into a toroid cavity nuclear magnetic resonance (NMR) imager. The concentration of solvated Li{sup +} ions in the carbon anode appears to be larger than in the bulk electrolyte, is substantially lower near the copper/carbon interface, and does not change with cell charging.

  4. An investigation of manganese based electrode materials for use in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sengupta, Surajit

    Lithium-based batteries are potential candidates to provide maximum volumetric and gravimetric energy density. One of the most attractive candidates as a cathode material for secondary lithium ion battery systems is the spinel LiMn 2O4 because it is environmentally friendly, less expensive and is capable of providing high energy density as compared to other cathode materials that are currently available. One problem associated with the spinel structure is capacity fading during multiple cycles of charge and discharge operations. This behaviour is due in part to the structural distortion during deep charge and discharge where nearly 100% of the lithium is extracted and inserted inside the spinel structure. Capacity fading can also be caused by dissolution of manganese ions in the electrolyte phase. A solution based method has been adapted for the synthesis of lithium manganese oxide, and chromium and cobalt doped mixed oxide materials using polyvinyl alcohol (PVA) as a chelating agent. It has been found from TGA/DSC analysis that at around 220°C the synthesis reaction is completed. The precursor powders obtained were annealed at different temperatures and times in the range of 250°C to 600°C and from 2 to 8 hours respectively to obtain pure spinel oxides. From X-ray analysis it has been observed that the crystallite size can be controlled in the range of approximately 6 nm to 32 nm depending on the annealing time and the temperature. The morphology of the synthesized materials consisted of submicron sized particles agglomerated with micropores inside the network structure. To observe the effect of physical properties on battery performance cyclic chronopotentiometric evaluation was conducted. It has been found with these synthesized materials that there is an increase in the 1st discharge capacity with an increase in the annealing time and the temperature at both 1C and C/5 rates. This increase is more significant when the annealing temperature is 600°C as

  5. Improved positive electrode materials for lithium-ion batteries: Exploring the high specific capacity of lithium cobalt dioxide and the high rate capability of lithium iron phosphate

    NASA Astrophysics Data System (ADS)

    Chen, Zhaohui

    During the past decade, the search for better electrode materials for Li-ion batteries has been of a great commercial interest, especially since Li-ion technology has become a major rechargeable battery technology with a market value of $3 billion US dollars per year. This thesis focuses on improving two positive electrode materials: one is a traditional positive electrode material--LiCoO2; the other is a new positive electrode material--LiFePO 4. Cho et al. reported that coating LiCoO2 with oxides can improve the capacity retention of LiCoO2 cycled to 4.4 V. The study of coatings in this thesis confirms this effect and shows that further improvement (30% higher energy density than that used in a commercial cell with excellent capacity retention) can be obtained. An in-situ XRD study proves that the mechanism of the improvement in capacity retention by coating proposed by Cho et al. is incorrect. Further experiments identify the suppression of impedance growth in the cell as the key reason for the improvement caused by coating. Based on this, other methods to improve the energy density of LiCoO2, without sacrificing capacity retention, are also developed. Using an XRD study, the structure of the phase between the O3-phase Li 1-xCoO2 (x > 0.5) and the O1 phase CoO2 was measured experimentally for the first time. XRD results confirmed the prediction of an H1-3 phase by Ceder's group. Apparently, because of the structural changes between the O3 phase and the H1-3 phase, good capacity retention cannot be attained for cycling LiCoO2 to 4.6 V with respect to Li metal. An effort was also made to reduce the carbon content in a LiFePO 4/C composite without sacrificing its rate capability. It was found that about 3% carbon by weight maintains both a good rate capability and a high pellet density for the composite.

  6. Laser printing and femtosecond laser structuring of electrode materials for the manufacturing of 3D lithium-ion micro-batteries

    NASA Astrophysics Data System (ADS)

    Smyrek, P.; Kim, H.; Zheng, Y.; Seifert, H. J.; Piqué, A.; Pfleging, W.

    2016-04-01

    Recently, three-dimensional (3D) electrode architectures have attracted great interest for the development of lithium-ion micro-batteries applicable for Micro-Electro-Mechanical Systems (MEMS), sensors, and hearing aids. Since commercial available micro-batteries are mainly limited in overall cell capacity by their electrode footprint, new processing strategies for increasing both capacity and electrochemical performance have to be developed. In case of such standard microbatteries, two-dimensional (2D) electrode arrangements are applied with thicknesses up to 200 μm. These electrode layers are composed of active material, conductive agent, graphite, and polymeric binder. Nevertheless, with respect to the type of active material, the active material to conductive agent ratio, and the film thickness, such thick-films suffer from low ionic and electronic conductivities, poor electrolyte accessibility, and finally, limited electrochemical performance under challenging conditions. In order to overcome these drawbacks, 3D electrode arrangements are under intense investigation since they allow the reduction of lithium-ion diffusion pathways in between inter-digitated electrodes, even for electrodes with enhanced mass loadings. In this paper, we present how to combine laser-printing and femtosecond laser-structuring for the development of advanced 3D electrodes composed of Li(Ni1/3Mn1/3Co1/3)O2 (NMC). In a first step, NMC thick-films were laser-printed and calendered to achieve film thicknesses in the range of 50 μm - 80 μm. In a second step, femtosecond laser-structuring was carried out in order to generate 3D architectures directly into thick-films. Finally, electrochemical cycling of laser-processed films was performed in order to evaluate the most promising 3D electrode designs suitable for application in long life-time 3D micro-batteries.

  7. The effects of electrode surface morphology on the actuation performance of IPMC

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Pugal, David; Leang, Kam K.; Kim, Kwang

    2013-04-01

    It is generally understood that increasing the specific surface area of the electrodes of IPMC leads to improved electromechanical performance of the material. Most physics based models compensate the effect of high surface area of the electrodes by increasing both diffusion constant and dielectric permittivity values, while using flat electrode approximation in calculations. Herein, a model was developed to take into account the shape and area of the electrodes. High surface area of the electrodes in the model was achieved by designing 2D polymer-electrode interface as a Koch fractal structure - different generation depths and both unidirectional and random directional generations were studied. The calculations indicate that increasing the generation depth of fractals, thus surface area of the electrodes results in more overall transported charge during the actuation process. Based on the model, the effect of the specific surface area of the electrodes on the electromechanical performance was experimentally investigated. IPMCs with different Pd-Pt electrode structures were prepared and their electromechanical and electrochemical properties were examined and discussed. The methods to manipulate the surface structure of Pd-Pt electrodes were proposed.

  8. A multilayered silicon-reduced graphene oxide electrode for high performance lithium-ion batteries.

    PubMed

    Gao, Xianfeng; Li, Jianyang; Xie, Yuanyuan; Guan, Dongsheng; Yuan, Chris

    2015-04-22

    A multilayered structural silicon-reduced graphene oxide electrode with superior electrochemical performance was synthesized from bulk Si particles through inexpensive electroless etching and graphene self-encapsulating approach. The prepared composite electrode presents a stable charge-discharge performance with high rate, showing a reversible capacity of 2787 mAh g(-1) at a charging rate of 100 mA g(-1), and a stable capacity over 1000 mAh g(-1) was retained at 1 A g(-1) after 50 cycles with a high columbic efficiency of 99% during the whole cycling process. This superior performance can be attributed to its novel multilayered structure with porous Si particles encapsulated, which can effectively accommodate the large volume change during the lithiation process and provide increased electrical conductivity. This facile low-cost approach offers a promising route to develop an optimized carbon encapsulated Si electrode for future industrial applications. PMID:25826636

  9. Plasma Sprayed Si Nano Composite Powders for Negative Electrode of Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Kaga, Mashiro; Hideshima, Tasuku; Kambara, Makoto

    The electrochemical performance of the Si nano composite powders produced by PS-PVD was analyzed with Li counter electrode. The PS-PVD powders have showed an improved capacity compared to the raw mg-Si as negative electrode. Furthermore composite powders produced with CH4 addition showed higher specific gravimetric capacities per Si active materials of 1200 mAh/g, compared to 1024 mAh/g for the powders without C, suggesting the effectiveness of C coating on to the primary nano-Si and SiC particle inclusion for reinforcement of the active materials.

  10. Conductive polymer foam surface improves the performance of a capacitive EEG electrode.

    PubMed

    Baek, Hyun Jae; Lee, Hong Ji; Lim, Yong Gyu; Park, Kwang Suk

    2012-12-01

    In this paper, a new conductive polymer foam-surfaced electrode was proposed for use as a capacitive EEG electrode for nonintrusive EEG measurements in out-of-hospital environments. The current capacitive electrode has a rigid surface that produces an undefined contact area due to its stiffness, which renders it unable to conform to head curvature and locally isolates hairs between the electrode surface and scalp skin, making EEG measurement through hair difficult. In order to overcome this issue, a conductive polymer foam was applied to the capacitive electrode surface to provide a cushioning effect. This enabled EEG measurement through hair without any conductive contact with bare scalp skin. Experimental results showed that the new electrode provided lower electrode-skin impedance and higher voltage gains, signal-to-noise ratios, signal-to-error ratios, and correlation coefficients between EEGs measured by capacitive and conventional resistive methods compared to a conventional capacitive electrode. In addition, the new electrode could measure EEG signals, while the conventional capacitive electrode could not. We expect that the new electrode presented here can be easily installed in a hat or helmet to create a nonintrusive wearable EEG apparatus that does not make users look strange for real-world EEG applications. PMID:22961261

  11. Lithium Redistribution in Lithium-Metal Batteries

    SciTech Connect

    Ferrese, A; Albertus, P; Christensen, J; Newman, J

    2012-01-01

    A model of a lithium-metal battery with a CoO2 positive electrode has been modeled in order to predict the movement of lithium in the negative electrode along the negative electrode/separator interface during cell cycling. A finite-element approach was used to incorporate an intercalation positive electrode using superposition, electrode tabbing, transport using concentrated solution theory, as well as the net movement of the lithium electrode during cycling. From this model, it has been found that movement of lithium along the negative electrode/separator interface does occur during cycling and is affected by three factors: the cell geometry, the slope of the open-circuit-potential function of the positive electrode, and concentration gradients in both the solid and liquid phases in the cell. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.027210jes] All rights reserved.

  12. Influence of electrode preparation on the electrochemical performance of LiNi0.8Co0.15Al0.05O2 composite electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Tran, Hai Yen; Greco, Giorgia; Täubert, Corina; Wohlfahrt-Mehrens, Margret; Haselrieder, Wolfgang; Kwade, Arno

    2012-07-01

    The electrode manufacturing for lithium-ion batteries is based on a complex process chain with several influencing factors. A proper tailoring of the electrodes can greatly improve both the electrochemical performances and the energy density of the battery. In the present work, some significant parameters during the preparation of LiNi0.8Co0.15Al0.05O2-based cathodes were investigated. The active material was mixed with a PVDF-binder and two conductive additives in different ratios. The electrode thickness, the degree of compacting and the conductive agent type and mixing ratio have proven to have a strong impact on the electrochemical performances of the composite electrodes, especially on their behaviour at high C-rates. Further it has been shown that the compacting has an essential influence on the mechanical properties of NCA coatings, according to their total, ductile and elastic deformation behaviour.

  13. Lithium titanate epitaxial coating on spinel lithium manganese oxide surface for improving the performance of lithium storage capability.

    PubMed

    Li, Jili; Zhu, Youqi; Wang, Lin; Cao, Chuanbao

    2014-11-12

    Spinel lithium titanate (Li4Ti5O12, LTO) is applied as an epitaxial coating layer on LiMn2O4 hollow microspheres (LMO) through solvothermal-assisted processing. The epitaxial interface between LTO and LMO can be clearly observed by high resolution transmission electron microscopy (HR-TEM) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with atomic resolution images. The epitaxial coating cathode (EC-LMO@LTO) exhibits an excellent cyclability, thermal and rate capability for LIBs cathode due to the complete, thin LTO coating layer with strong adhesion to the host material. In addition, the small structure mismatch and high Li(+)-ion mobility of LTO can be beneficial to forming an efficient tunnel for Li(+)-ion transfer at the interface. It is suggested that EC-LMO@LTO can be recognized as a promising cathode material in electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). PMID:25322171

  14. Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries using Synchrotron Radiation Techniques

    SciTech Connect

    Mehta, Apurva; Stanford Synchrotron Radiation Lightsource; Doeff, Marca M.; Chen, Guoying; Cabana, Jordi; Richardson, Thomas J.; Mehta, Apurva; Shirpour, Mona; Duncan, Hugues; Kim, Chunjoong; Kam, Kinson C.; Conry, Thomas

    2013-04-30

    We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li ion and Na ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices.

  15. Binder-free network-enabled MoS2-PPY-rGO ternary electrode for high capacity and excellent stability of lithium storage

    NASA Astrophysics Data System (ADS)

    Xie, D.; Wang, D. H.; Tang, W. J.; Xia, X. H.; Zhang, Y. J.; Wang, X. L.; Gu, C. D.; Tu, J. P.

    2016-03-01

    A unique MoS2-based composite composed of MoS2 nanosheets wrapped by a conductive polypyrrole (PPY) layer and closely incorporated within reduced graphene oxide (rGO) nanosheets is prepared by all-solution method. As a free-binder electrode for lithium-ion batteries, the ternary electrode delivers an initial discharge capacity of 1428 mAh g-1, maintains 1070 mAh g-1 after 400 cycles at a current density of 200 mA g-1, and also exhibits superior rate capacity of 600 mAh g-1 at a high current density of 2000 A g-1. The enhanced electrochemical performance is attributed to the advantageous combination of the 3D hierarchically rGO skeleton and in-situ formed conductive PPY coating. This design route represents a new direction for high-performance lithium ion batteries and related energy storage application with advanced nanostructured materials.

  16. Restructuring of an Ir(210) electrode surface by potential cycling

    PubMed Central

    Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

    2014-01-01

    Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

  17. Novel hierarchical three-dimensional ammonium vanadate nanowires electrodes for lithium ion battery

    NASA Astrophysics Data System (ADS)

    Fang, Dong; Cao, Yunhe; Liu, Ruina; Xu, Weilin; Liu, Suqin; Luo, Zhiping; Liang, Chaowei; Liu, Xiaoqing; Xiong, Chuanxi

    2016-01-01

    Ammonium vanadate (NH4V4O10) nanowire flowers and nanowires on titanium (Ti) foils are synthesized by hexamethylenetetramine (HMTA)-assisted hydrothermal reactions as a cathode material for lithium-ion battery. The as-prepared NH4V4O10 nanowires are about 50 nm in diameter and several micrometers in length. The effects of reaction time, temperature and additive concentration on the resulting morphology are investigated. Reversible lithium intercalation behavior of the nanowires has been evaluated by cyclic voltammetry and galvanostatic discharge-charge cycling. The NH4V4O10 nanowires on Ti foil deliver a high discharge capacity of 168.5 mA h g-1 after 100 cycles between 2.0 and 4.0 V at 50 mA g-1. A high rate capability is obtained with a remaining discharge capacity of about 182.6 mA h g-1 after 35 cycles at various rates. Further, the NH4V4O10 nanowires on Ti foil have a higher discharge capacity of 330.5 mA h g-1 after 100 cycles at 0.8-4.0 V at 50 mA g-1.

  18. Airflow acceleration performance of asymmetric surface dielectric barrier discharge actuators at different exposed needle electrode heights

    NASA Astrophysics Data System (ADS)

    Yang, Liang; Yan, Hui-Jie; Qi, Xiao-Hua; Hua, Yue; Ren, Chun-Sheng

    2015-12-01

    The use of plasma, created by asymmetric surface dielectric barrier discharge (ASDBD), as aerodynamic actuators to control airflows, has been of widespread concern over the past decades. For the single ASDBD, the actuator performance is dependent on the geometry of actuator and the produced plasma. In this work, a new electrode configuration, i.e., a row of needle, is taken as an exposed electrode for the ASDBD plasma actuator, and the electrode height is adjustable. The effects of different electrode heights on the airflow acceleration behavior are experimentally investigated by measuring surface potential distribution, ionic wind velocity, and mean thrust force production. It is demonstrated that the airflow velocity and thrust force increase with the exposed electrode height and the best actuator performance can be obtained when the exposed electrode is adjusted to an appropriate height. The difference, as analyzed, is mainly due to the distinct plasma spatial distributions at different exposed electrode heights.

  19. The effect of CoSn/CoSn 2 phase ratio on the electrochemical behaviour of Sn 40Co 40C 20 ternary alloy electrodes in lithium cells

    NASA Astrophysics Data System (ADS)

    Hassoun, J.; Ochal, P.; Panero, S.; Mulas, G.; Bonatto Minella, C.; Scrosati, B.

    Samples of a SnCoC-based electrodes, all having the molar composition Sn 40Co 40C 20, but differing by the high energy ball milling synthesis conditions, have been tested in lithium cells. The investigation was carried out by using a series of complementary techniques, including potentiodynamic cycling with galvanostatic acceleration, galvanostatic charge-discharge cycling and impedance spectroscopy. The results confirmed the high capacity delivery of this type of ternary electrodes but also revealed that their electrochemical behaviour is influenced by the relative abundance of the nanosized domains of CoSn and CoSn 2 in their structure.

  20. First principle study of the surface reactivity of layered lithium oxides LiMO2 (M = Ni, Mn, Co)

    NASA Astrophysics Data System (ADS)

    Vallverdu, Germain; Minvielle, Marie; Andreu, Nathalie; Gonbeau, Danielle; Baraille, Isabelle

    2016-07-01

    LiNixMnyCo1 - x - yO2 compounds (NMC) are layered oxides widely used in commercial lithium-ion batteries at the positive electrode. Nevertheless surface reactivity of this material is still not well known. As a first step, based on first principle calculations, this study deals with the electronic properties and the surface reactivity of LiMO2 (M = Co, Ni, Mn) compounds, considering the behavior of each transition metal separately in the same R 3 ̅ mα-NaFeO2-type structure, the one of LiCoO2 and NMC. For each compound, after a brief description of the bare slab electronic properties, we explored the acido-basic and redox properties of the (110) and (104) surfaces by considering the adsorption of a gaseous probe. The chemisorption of SO2 produces both sulfite or sulfate species associated respectively to an acido-basic or a reduction process. These processes are localized on the transition metals of the first two layers of the surface. Although sulfate species are globally favored, a different behavior is obtained depending on both the surface and the transition metal considered. We conclude with a simple scheme which describes the reduction processes on the both surfaces in terms of formal oxidation degrees of transition metals.

  1. Synthesis and electrochemical properties of Li(1.3)Nb(0.3)V(0.4)O2 as a positive electrode material for rechargeable lithium batteries.

    PubMed

    Yabuuchi, Naoaki; Takeuchi, Mitsue; Komaba, Shinichi; Ichikawa, Shinnosuke; Ozaki, Tetsuya; Inamasu, Tokuo

    2016-02-01

    The binary system, xLi3NbO4-(1 - x)LiVO2, was first examined as an electrode material for rechargeable lithium batteries. The sample (x = 0.43) crystallizes into a cation-disordered rocksalt structure and delivers a reversible capacity of ca. 230 mA h g(-1), which originates from V(3+)/V(5+) redox with electrochemically inactive niobium ions. PMID:26686804

  2. 3D macroporous electrode and high-performance in lithium-ion batteries using SnO2 coated on Cu foam

    NASA Astrophysics Data System (ADS)

    Um, Ji Hyun; Choi, Myounggeun; Park, Hyeji; Cho, Yong-Hun; Dunand, David C.; Choe, Heeman; Sung, Yung-Eun

    2016-01-01

    A three-dimensional porous architecture makes an attractive electrode structure, as it has an intrinsic structural integrity and an ability to buffer stress in lithium-ion batteries caused by the large volume changes in high-capacity anode materials during cycling. Here we report the first demonstration of a SnO2-coated macroporous Cu foam anode by employing a facile and scalable combination of directional freeze-casting and sol-gel coating processes. The three-dimensional interconnected anode is composed of aligned microscale channels separated by SnO2-coated Cu walls and much finer micrometer pores, adding to surface area and providing space for volume expansion of SnO2 coating layer. With this anode, we achieve a high reversible capacity of 750 mAh g-1 at current rate of 0.5 C after 50 cycles and an excellent rate capability of 590 mAh g-1 at 2 C, which is close to the best performance of Sn-based nanoscale material so far.

  3. X-ray photoelectron spectroscopy of negative electrodes from high-power lithium-ion cells showing various levels of power fade

    SciTech Connect

    Herstedt, Marie; Abraham, Daniel P.; Kerr, John B.

    2004-02-28

    High-power lithium-ion cells for transportation applications are being developed and studied at Argonne National Laboratory. The current generation of cells containing LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2}-based cathodes, graphite-based anodes, and LiPF6-based electrolytes show loss of capacity and power during accelerated testing at elevated temperatures. Negative electrode samples harvested from some cells that showed varying degrees of power and capacity fade were examined by X-ray photoelectron spectroscopy (XPS). The samples exhibited a surface film on the graphite, which was thicker on samples from cells that showed higher fade. Furthermore, solvent-based compounds were dominant on samples from low power fade cells, whereas LiPF{sub 6}-based products were dominant on samples from high power fade cells. The effect of sample rinsing and air exposure is discussed. Mechanisms are proposed to explain the formation of compounds suggested by the XPS data.

  4. 3D macroporous electrode and high-performance in lithium-ion batteries using SnO2 coated on Cu foam

    PubMed Central

    Um, Ji Hyun; Choi, Myounggeun; Park, Hyeji; Cho, Yong-Hun; Dunand, David C.; Choe, Heeman; Sung, Yung-Eun

    2016-01-01

    A three-dimensional porous architecture makes an attractive electrode structure, as it has an intrinsic structural integrity and an ability to buffer stress in lithium-ion batteries caused by the large volume changes in high-capacity anode materials during cycling. Here we report the first demonstration of a SnO2-coated macroporous Cu foam anode by employing a facile and scalable combination of directional freeze-casting and sol-gel coating processes. The three-dimensional interconnected anode is composed of aligned microscale channels separated by SnO2-coated Cu walls and much finer micrometer pores, adding to surface area and providing space for volume expansion of SnO2 coating layer. With this anode, we achieve a high reversible capacity of 750 mAh g−1 at current rate of 0.5 C after 50 cycles and an excellent rate capability of 590 mAh g−1 at 2 C, which is close to the best performance of Sn-based nanoscale material so far. PMID:26725652

  5. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    NASA Astrophysics Data System (ADS)

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-02-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results.

  6. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    PubMed Central

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-01-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results. PMID:26916054

  7. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices.

    PubMed

    Soliman, Ahmed B; Abdel-Samad, Hesham S; Abdel Rehim, Sayed S; Hassan, Hamdy H

    2016-01-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results. PMID:26916054

  8. Toward a stabilized lattice framework and surface structure of layered lithium-rich cathode materials with Ti modification.

    PubMed

    Wang, Sihui; Li, Yixiao; Wu, Jue; Zheng, Bizhu; McDonald, Matthew J; Yang, Yong

    2015-04-21

    Layered lithium-rich oxides have several serious shortcomings such as fast voltage fading and poor cyclic stability of energy density which greatly hinder their practical applications. Fabrication of a stable framework of layered lithium-rich oxides during charging-discharging is crucial for addressing the above problems. In this work, we show that Ti modification is a promising way to realize this target with bifunctional roles. For example, it is able to substitute Mn in the lattice framework and form a stable surface layer. It therefore leads to an improved retention of energy density of the Ti-modified Li1.2Mn0.54-xTixNi0.13Co0.13O2 (x = 0.04, 0.08, and 0.15) materials during cycling. The evolution of dQ/dV curves show that the layered/spinel phase transformation is suppressed owing to the introduction of strong Ti-O bonds in the framework. In addition, SEM, TEM, and EIS results confirm that a more uniform and stable interface layer is formed on Ti-modified Li1.2Mn0.54-xTixNi0.13Co0.13O2 (x = 0.04, 0.08, and 0.15) materials compared with the Ti-free counterpart. The stable interface layer on the lithium-rich oxides is also beneficial for further reducing side reactions, resulting in stable interface layer resistance. Therefore, the improved cycling performance of the material is due to both contribution of the more stable framework and enhanced electrode/electrolyte interface by Ti modification. PMID:25790778

  9. Low-temperature synthesis of CuO-interlaced nanodiscs for lithium ion battery electrodes

    PubMed Central

    2011-01-01

    In this study, we report the high-yield synthesis of 2-dimensional cupric oxide (CuO) nanodiscs through dehydrogenation of 1-dimensional Cu(OH)2 nanowires at 60°C. Most of the nanodiscs had a diameter of approximately 500 nm and a thickness of approximately 50 nm. After further prolonged reaction times, secondary irregular nanodiscs gradually grew vertically into regular nanodiscs. These CuO nanostructures were characterized using X-ray diffraction, transmission electron microscopy, and Brunauer-Emmett-Teller measurements. The possible growth mechanism of the interlaced disc CuO nanostructures is systematically discussed. The electrochemical performances of the CuO nanodisc electrodes were evaluated in detail using cyclic voltammetry and galvanostatic cycling. Furthermore, we demonstrate that the incorporation of multiwalled carbon nanotubes enables the enhanced reversible capacities and capacity retention of CuO nanodisc electrodes on cycling by offering more efficient electron transport paths. PMID:21711916

  10. Study on microstructures of electrodes in lithium-ion batteries using variational multi-scale enrichment

    NASA Astrophysics Data System (ADS)

    Lee, Sangmin; Sastry, Ann Marie; Park, Jonghyun

    2016-05-01

    Performance and degradation of a Li-ion battery reflect the transport and kinetics of related species within the battery's electrode microstructures. The variational multi-scale principle is adapted to a Li-ion battery system in order to improve the predictions of battery performance by including multi-scale and multiphysics phenomena among the particle aggregates in the electrode; this physics cannot be addressed by conventional homogenized approaches. The developed model is verified through the direct numerical solutions and compared with the conventional pseudo-2D (P2D) model method. The developed model has revealed more dynamic battery behaviors related to the variation of the microstructure-such as particle shape, tortuosity, and material composition-while the corresponding result from P2D shows a monotonous change within different structures.

  11. Low-temperature synthesis of CuO-interlaced nanodiscs for lithium ion battery electrodes

    NASA Astrophysics Data System (ADS)

    Seo, Seung-Deok; Jin, Yun-Ho; Lee, Seung-Hun; Shim, Hyun-Woo; Kim, Dong-Wan

    2011-05-01

    In this study, we report the high-yield synthesis of 2-dimensional cupric oxide (CuO) nanodiscs through dehydrogenation of 1-dimensional Cu(OH)2 nanowires at 60°C. Most of the nanodiscs had a diameter of approximately 500 nm and a thickness of approximately 50 nm. After further prolonged reaction times, secondary irregular nanodiscs gradually grew vertically into regular nanodiscs. These CuO nanostructures were characterized using X-ray diffraction, transmission electron microscopy, and Brunauer-Emmett-Teller measurements. The possible growth mechanism of the interlaced disc CuO nanostructures is systematically discussed. The electrochemical performances of the CuO nanodisc electrodes were evaluated in detail using cyclic voltammetry and galvanostatic cycling. Furthermore, we demonstrate that the incorporation of multiwalled carbon nanotubes enables the enhanced reversible capacities and capacity retention of CuO nanodisc electrodes on cycling by offering more efficient electron transport paths.

  12. Integrated 3D porous C-MoS2/nitrogen-doped graphene electrode for high capacity and prolonged stability lithium storage

    NASA Astrophysics Data System (ADS)

    Xie, D.; Tang, W. J.; Xia, X. H.; Wang, D. H.; Zhou, D.; Shi, F.; Wang, X. L.; Gu, C. D.; Tu, J. P.

    2015-11-01

    Scrupulous design and fabrication of advanced anode materials are of great importance for developing high-performance lithium ion batteries. Herein, we report a facile strategy for construction of free-standing and free-binder 3D porous carbon coated MoS2/nitrogen-doped graphene (C-MoS2/N-G) integrated electrode via a hydrothermal-induced self-assembly process. The preformed carbon coated MoS2 is strongly anchored on the porous nitrogen-doped graphene aerogel architecture. As an anode for lithium ion batteries, the C-MoS2/N-G electrode delivers a high first discharge capacity of 1600 mAh g-1 and maintains 900 mAh g-1 after 500 cycles at a current density of 200 mA g-1. Impressively, superior high-rate capability is achieved for the C-MoS2/N-G with a reversible capacity of 500 mAh g-1 at a high current density of 4000 mA g-1. Furthermore, the lithium storage mechanism of the obtained integrated electrode is investigated by ex-situ X-ray photoelectron spectroscopy and transmission electron microscopy in detail.

  13. 3D Porous Sponge-Inspired Electrode for Stretchable Lithium-Ion Batteries.

    PubMed

    Liu, Wei; Chen, Zheng; Zhou, Guangmin; Sun, Yongming; Lee, Hye Ryoung; Liu, Chong; Yao, Hongbin; Bao, Zhenan; Cui, Yi

    2016-05-01

    A stretchable Li4 Ti5 O12 anode and a LiFePO4 cathode with 80% stretchability are prepared using a 3D interconnected porous polydimethylsiloxane sponge based on sugar cubes. 82% and 91% capacity retention for anode and cathode are achieved after 500 stretch-release cycles. Slight capacity decay of 6% in the battery using the electrode in stretched state is observed. PMID:26992146

  14. High surface area electrodes by template-free self-assembled hierarchical porous gold architecture.

    PubMed

    Morag, Ahiud; Golub, Tatiana; Becker, James; Jelinek, Raz

    2016-06-15

    The electrode active surface area is a crucial determinant in many electrochemical applications and devices. Porous metal substrates have been employed in electrode design, however construction of such materials generally involves multistep processes, generating in many instances electrodes exhibiting incomplete access to internal pore surfaces. Here we describe fabrication of electrodes comprising hierarchical, nano-to-microscale porous gold matrix, synthesized through spontaneous crystallization of gold thiocyanate in water. Cyclic voltammetry analysis revealed that the specific surface area of the conductive nanoporous Au microwires was very high and depended only upon the amount of gold used, not electrode areas or geometries. Application of the electrode in a pseudo-capacitor device is presented. PMID:27016632

  15. A Spectroscopic Measurement of Recycling on the Surface of a Liquid Lithium Limiter in CDX-U

    NASA Astrophysics Data System (ADS)

    Marfuta, P.; Kaita, R.; Majeski, R.; Soukhanovskii, V.; Maingi, R.

    2003-10-01

    Spectroscopic measurements of lithium plasma-facing surfaces should give a quantitative assessment of the local recycling in CDX-U. We will use both a 1-D CCD camera with an interference filter and a pair of fiber-optic filterscopes focused on different parts of a fully-toroidal liquid lithium limiter tray. Additional filterscope data will be taken along a sightline immediately above the tray, so that the edge plasma emission can be subtracted from the direct views of the lithium surface. The diagnostics will measure the H-alpha line both with and without lithium in the limiter tray to assess the reduction of neutral hydrogen recycling, as well as the Li-I emission to observe the level of lithium introduced into the plasma, and the C-III and O-II lines to measure the effect of the lithium on plasma impurities.

  16. Linking PFC surface characteristics and plasma performance in the Lithium Tokamak Experiment

    NASA Astrophysics Data System (ADS)

    Lucia, M.; Kaita, R.; Majeski, R.; Boyle, D. P.; Jaworski, M. A.; Schmitt, J. C.; Bedoya, F.; Allain, J. P.

    2015-11-01

    The Lithium Tokamak Experiment (LTX) is a spherical torus magnetic confinement device designed to accommodate lithium as the primary plasma-facing component (PFC). Results are presented from the implementation on LTX of the Materials Analysis and Particle Probe (MAPP), a compact in vacuo surface science diagnostic. With MAPP, in situ surface analysis techniques of x-ray photoelectron spectroscopy and thermal desorption spectroscopy are used to study evolution of the PFC surface chemistry in LTX as a function of varied lithium coating, hydrogen plasma exposure, and PFC surface temperature (20 - 300°C). Surface analysis results are then correlated with various measures of LTX plasma performance, including toroidal plasma current, line-integrated plasma density, and density-normalized impurity emission. Lithium coatings are observed to convert within hours to Li2O by gettering oxygen from both the residual vacuum and the PFC substrate. However, plasma performance remains elevated even with discharges operating against Li2O -coated PFCs. Hydrogen is retained by these Li2O coatings during a discharge, but it is almost completely desorbed as outgassed H2 in the minutes following the discharge; no persistent LiH formation is observed. This work was supported by U.S. DOE contracts DE-AC02-09CH11466, DE-AC52-07NA27344, and DE-SC0010717, as well as by an NSF GRFP fellowship under grant DGE-0646086.

  17. Manipulating the Surface Reactions in Lithium Sulfur Batteries Using Hybrid Anode Structures

    SciTech Connect

    Huang, Cheng; Xiao, Jie; Shao, Yuyan; Zheng, Jianming; Bennett, Wendy D.; Lu, Dongping; Saraf, Laxmikant V.; Engelhard, Mark H.; Ji, Liwen; Zhang, Jiguang; Li, Xiaolin; Graff, Gordon L.; Liu, Jun

    2014-01-09

    Lithium-sulfur (Li-S) batteries have recently attracted extensive attention due to the high theoretical energy density and potential low cost. Even so, significant challenges prevent widespread adoption, including continuous dissolution and consumption of active sulfur during cycling. Here we present a fundamentally new design using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on the anode. The lithiated graphite placed in front of the lithium metal functions as an artificial self-regulated solid electrolyte interface (SEI) layer to actively control the electrochemical reaction while minimizing the deleterious side reactions on the surface and bulk lithium metal. Continuous corrosion and contamination of lithium anode by dissolved polysulfides is largely mitigated. Excellent electrochemical performance has been observed. Li-S cell incorporating the hybrid design retain a capacity of more than 800 mAh g-1 for 400 cycles, corresponding to only 11% fade and a Coulombic efficiency above 99%. This simple hybrid concept may also provide new lessons for protecting metal anodes in other energy storage devices.

  18. Mixed ion/electron-conductive protective soft nanomatter-based conformal surface modification of lithium-ion battery cathode materials

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    Understanding and control of interfacial phenomena between electrode material and liquid electrolytes are of major scientific importance for boosting development of high-performance lithium ion batteries with reliable electrochemical/safety attributes. Here, as an innovative surface engineering approach to address the interfacial issues, a new concept of mixed ion/electron-conductive soft nanomatter-based conformal surface modification of the cathode material is presented. The soft nanomatter is comprised of an electron conductive carbonaceous (C) substance embedded in an ion conductive polyimide (PI) nanothin compliant film. In addition to its structural uniqueness, the newly proposed surface modification benefits from a simple fabrication process. The PI/carbon soft nanomatter is directly synthesized on LiCoO2 surface via one-pot thermal treatment of polyamic acid (=PI precursor) and sucrose (=carbon source) mixture, where the LiCoO2 powders are chosen as a model system to explore the feasibility of this surface engineering strategy. The resulting PI/carbon coating layer facilitates electronic conduction and also suppresses unwanted side reactions arising from the cathode material-liquid electrolyte interface. These synergistic coating effects of the multifunctional PI/carbon soft nanomatter significantly improve high-voltage cell performance and also mitigate interfacial exothermic reaction between cathode material and liquid electrolyte.

  19. Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries

    DOEpatents

    Deng, Haixia; Belharouak, Ilias; Amine, Khalil

    2012-10-02

    Nano-sized structured dense and spherical layered positive active materials provide high energy density and high rate capability electrodes in lithium-ion batteries. Such materials are spherical second particles made from agglomerated primary particles that are Li.sub.1+.alpha.(Ni.sub.xCo.sub.yMn.sub.z).sub.1-tM.sub.tO.sub.2-dR.sub.d- , where M is selected from can be Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof, R is selected from F, Cl, Br, I, H, S, N, or a mixture of any two or more thereof, and 0.ltoreq..alpha..ltoreq.0.50; 0

  20. Platinum electrode modification: Unique surface carbonization approach to improve performance and sensitivity.

    PubMed

    Lee, Hwi Yong; Barber, Cedrick; Minerick, Adrienne R

    2015-08-01

    Many microfluidic devices, also known as lab-on-a-chip devices, employ electrochemical detection methods using microelectrodes. Miniaturizing electrodes inevitably reduces electrode sensitivity and decreases the S/N, which limits applications within microfluidic devices. However, microelectrode surface modification can increase the surface area and sensitivity. In the present work, we report substantial improvement in platinum electrode performance and sensitivity by coating with carbon from red blood cells. The larger goal of this work was to measure DC electrical resistances of red blood cell suspensions in a microchannel for hematocrit determination. It was observed that as current responses of red blood cell suspensions were measured, the platinum electrode performance (reproducibility and S/N) improved with time. The platinum electrode electrocatalytic activity for red blood cell current measurements improved by 140%. Systematic experimentation revealed that red blood cells adsorb and carbonize the platinum electrode surfaces. The electrode surfaces before and after performance improvements were analyzed by field emission scanning electron microscopy, energy dispersive spectrometry, and Raman spectrometry. The formed carbon layers on the electrode surfaces were found to be proteomic and increased surface area with a porous three-dimensional structure, thus improving performance and stabilizing currents. PMID:26032065

  1. Do surface electrode recordings validly represent latissimus dorsi activation patterns during shoulder tasks?

    PubMed

    Ginn, Karen A; Halaki, Mark

    2015-02-01

    Because of its superficial location surface electrodes are commonly used to record latissimus dorsi (LD) activity. Despite the fact that the recommended electrode placement is over the belly where LD is quite thin no studies have investigated the possibility of signal contamination from muscles lying deep to LD. Therefore, the aim of this study was to determine the validity of using surface electrodes to record activity from LD. Eight asymptomatic subjects performed ramped isometric (0-100% maximum load) and dynamic (70% maximum load) shoulder tasks. Intramuscular electrodes were inserted into LD and the adjacent erector spinae. Surface electrodes were placed over LD around the intramuscular electrodes. Results indicated that while there was no difference in activity level or activation pattern (ICC>0.94) recorded by the two electrode types during shoulder tasks in which LD would be expected to be active (extension and adduction), significantly lower (p<0.05) LD activity was recorded via intramuscular electrodes during the shoulder flexion and abduction tasks. Therefore, recordings of LD activity by surface electrodes overestimate LD activity during shoulder tasks when this muscle would be expected to be activated at minimum levels. Erector spinae immediately deep to LD was confirmed as a source of crosstalk contamination. PMID:25467544

  2. Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

    PubMed

    Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

    2016-06-29

    High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively. PMID:26961230

  3. Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

    PubMed

    Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

    2014-07-21

    Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation. PMID:24782218

  4. High Conductivity Water Treatment Using Water Surface Discharge with Nonmetallic Electrodes

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoping; Zhang, Xingwang; Lei, Lecheng

    2013-06-01

    Although electrohydraulic discharge is effective for wastewater treatment, its application is restricted by water conductivity and limited to the treatment of low conductivity water. For high conductivity water treatment, water-surface discharge is the preferred choice. However, the metallic electrodes are easily corroded because of the high temperature and strong oxidative environment caused by gas phase discharge and the electrochemical reaction in water. As a result, the efficiency of the water treatment might be affected and the service life of the reactor might be shortened. In order to avoid the corrosion problem, nonmetallic electrode water-surface discharge is introduced into high conductivity water treatment in the present study. Carbon-felt and water were used as the high voltage electrode and ground electrode, respectively. A comparison of the electrical and chemical characteristics showed that nonmetallic electrode discharge maintained the discharge characteristics and enhanced the energy efficiency, and furthermore, the corrosion of metal electrodes was avoided.

  5. Germanium microflower-on-nanostem as a high-performance lithium ion battery electrode

    PubMed Central

    Lee, Gwang-Hee; Kwon, S. Joon; Park, Kyung-Soo; Kang, Jin-Gu; Park, Jae-Gwan; Lee, Sungjun; Kim, Jae-Chan; Shim, Hyun-Woo; Kim, Dong-Wan

    2014-01-01

    We demonstrate a new design of Ge-based electrodes comprising three-dimensional (3-D) spherical microflowers containing crystalline nanorod networks on sturdy 1-D nanostems directly grown on a metallic current collector by facile thermal evaporation. The Ge nanorod networks were observed to self-replicate their tetrahedron structures and form a diamond cubic lattice-like inner network. After etching and subsequent carbon coating, the treated Ge nanostructures provide good electrical conductivity and are resistant to gradual deterioration, resulting in superior electrochemical performance as anode materials for LIBs, with a charge capacity retention of 96% after 100 cycles and a high specific capacity of 1360 mA h g−1 at 1 C and a high-rate capability with reversible capacities of 1080 and 850 mA h g−1 at the rates of 5 and 10 C, respectively. The improved electrochemical performance can be attributed to the fast electron transport and good strain accommodation of the carbon-filled Ge microflower-on-nanostem hybrid electrode. PMID:25363317

  6. Radiation effects on the electrode and electrolyte of a lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Tan, Chuting; Lyons, Daniel J.; Pan, Ke; Leung, Kwan Yee; Chuirazzi, William C.; Canova, Marcello; Co, Anne C.; Cao, Lei R.

    2016-06-01

    The performance degradation and durability of a Li-ion battery is a major concern when it is operated under radiation conditions, for instance, in deep space exploration, in high radiation field, or rescuing or sampling equipment in a post-nuclear accident scenario. This paper examines the radiation effects on the electrode and electrolyte materials separately and their effects on a battery's capacity loss and resistance increase. A60Co irradiator (34.3 krad/h) was used to provide 0.8, 4.1, and 9.8 Mrad dose to LiFePO4 electrodes and 0.8, 1.6, and 5.7 Mrad to 1 M LiPF6 in 1:1 wt% EC:DMC electrolytes. This study shows that the coin cells assembled with irradiated components have higher failure rate (ca. 70%) than that of control group (ca. 14%). A significant battery capacity fade post irradiation was observed. The electrolyte also shows a darkened color a few weeks or months after irradiation. The discovery of this latent effect may be significant because a battery may degrade significantly even showing no sign of degradation immediately after exposure. We investigated electrolyte composition by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and nuclear magnetic resonance spectroscopy prior and post irradiation. Polymerization reactions and HF formation are considered as the cause of the discoloration.

  7. Germanium microflower-on-nanostem as a high-performance lithium ion battery electrode

    NASA Astrophysics Data System (ADS)

    Lee, Gwang-Hee; Kwon, S. Joon; Park, Kyung-Soo; Kang, Jin-Gu; Park, Jae-Gwan; Lee, Sungjun; Kim, Jae-Chan; Shim, Hyun-Woo; Kim, Dong-Wan

    2014-11-01

    We demonstrate a new design of Ge-based electrodes comprising three-dimensional (3-D) spherical microflowers containing crystalline nanorod networks on sturdy 1-D nanostems directly grown on a metallic current collector by facile thermal evaporation. The Ge nanorod networks were observed to self-replicate their tetrahedron structures and form a diamond cubic lattice-like inner network. After etching and subsequent carbon coating, the treated Ge nanostructures provide good electrical conductivity and are resistant to gradual deterioration, resulting in superior electrochemical performance as anode materials for LIBs, with a charge capacity retention of 96% after 100 cycles and a high specific capacity of 1360 mA h g-1 at 1 C and a high-rate capability with reversible capacities of 1080 and 850 mA h g-1 at the rates of 5 and 10 C, respectively. The improved electrochemical performance can be attributed to the fast electron transport and good strain accommodation of the carbon-filled Ge microflower-on-nanostem hybrid electrode.

  8. Germanium microflower-on-nanostem as a high-performance lithium ion battery electrode.

    PubMed

    Lee, Gwang-Hee; Kwon, S Joon; Park, Kyung-Soo; Kang, Jin-Gu; Park, Jae-Gwan; Lee, Sungjun; Kim, Jae-Chan; Shim, Hyun-Woo; Kim, Dong-Wan

    2014-01-01

    We demonstrate a new design of Ge-based electrodes comprising three-dimensional (3-D) spherical microflowers containing crystalline nanorod networks on sturdy 1-D nanostems directly grown on a metallic current collector by facile thermal evaporation. The Ge nanorod networks were observed to self-replicate their tetrahedron structures and form a diamond cubic lattice-like inner network. After etching and subsequent carbon coating, the treated Ge nanostructures provide good electrical conductivity and are resistant to gradual deterioration, resulting in superior electrochemical performance as anode materials for LIBs, with a charge capacity retention of 96% after 100 cycles and a high specific capacity of 1360 mA h g(-1) at 1 C and a high-rate capability with reversible capacities of 1080 and 850 mA h g(-1) at the rates of 5 and 10 C, respectively. The improved electrochemical performance can be attributed to the fast electron transport and good strain accommodation of the carbon-filled Ge microflower-on-nanostem hybrid electrode. PMID:25363317

  9. Nano crystalline TiO2 thin films as negative electrodes for lithium ion batteries.

    PubMed

    Aslan, Serdar; Guler, Mehmet Oguz; Cevher, Ozgur; Akbulut, Hatem

    2012-12-01

    In this study, rutile (tetragonal, P42/mnm), anatase (tetragonal, I41/amd) polymorphs of titanium dioxide films were synthesized successfully magnetron sputtering of titanium films on stainless steel substrates followed by in situ direct current plasma oxidation. The as-prepared titanium dioxide thin films were oxidized at 75 W, 100 W and 125 W plasma powers in order to optimize the system with best electrochemical performance. The mean grain sizes of the deposited films were found to be in the range of 14.2-12.9 nm as revealed by the scanning electron microscopy and X-ray diffractometer studies. The electrochemical studies were performed with pure metallic lithium foil cathode with the best performing nano structured titanium dioxide as anode. The specific capacity of the nanocrystalline titanium dioxide films oxidized at 125 W direct current was 207 mA h g(-1) even after 20 cycles in the 0.02-2 V region, indicating excellent cycling stability and reversibility. PMID:23447985

  10. Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation

    NASA Astrophysics Data System (ADS)

    Brady, Nicholas W.; Knehr, K. W.; Cama, Christina A.; Lininger, Christianna N.; Lin, Zhou; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; West, Alan C.

    2016-07-01

    Magnetite is a known lithium intercalation material, and the loss of active, nanocrystalline magnetite can be inferred from the open-circuit potential relaxation. Specifically, for current interruption after relatively small amounts of lithium insertion, the potential first increases and then decreases, and the decrease is hypothesized to be due to a formation of a surface layer, which increases the solid-state lithium concentration in the remaining active material. Comparisons of simulation to experiment suggest that the reactions with the electrolyte result in the formation of a thin layer of electrochemically inactive material, which is best described by a nucleation and growth mechanism. Simulations are consistent with experimental results observed for 6, 8 and 32-nm crystals. Furthermore, simulations capture the experimental differences in lithiation behavior between the first and second cycles.

  11. Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation

    DOE PAGESBeta

    Nicholas W. Brady; Takeuchi, Esther S.; Knehr, K. W.; Cama, Christina A.; Lininger, Christianna N.; Lin, Zhou; Marschilok, Amy C.; Takeuchi, Kenneth J.; West, Alan C.

    2016-05-05

    Magnetite is a known lithium intercalation material, and the loss of active, nanocrystalline magnetite can be inferred from the open-circuit potential relaxation. Specifically, for current interruption after relatively small amounts of lithium insertion, the potential first increases and then decreases, and the decrease is hypothesized to be due to a formation of a surface layer, which increases the solid-state lithium concentration in the remaining active material. Comparisons of simulation to experiment suggest that the reactions with the electrolyte result in the formation of a thin layer of electrochemically inactive material, which is best described by a nucleation and growth mechanism.more » Simulations are consistent with experimental results observed for 6, 8 and 32-nm crystals. As a result, simulations capture the experimental differences in lithiation behavior between the first and second cycles.« less

  12. Lithium: Is It Possible to Generate It at the Stellar Surfaces?

    NASA Astrophysics Data System (ADS)

    Gopka, V. F.; Yushchenko, A. V.; Shavrina, A. V.; Yushchenko, V. A.

    2014-08-01

    The possible mechanisms of lithium production in stars of different types and ages remain completely unidentified up to now. We proposed the scenario of lithium production in multiple stellar systems at the evolutionary stages when one of the components is a young neutron star (NS). In this case the source of lithium is the result of irradiation of surface of optical star by high-energy particles accelerated to relativistic velocities in the inner parts of the accretion disk around a NS. We show that the understanding of the evolutionary phase of Li-rich stars is impossible without the understanding of evolutionary state of stars, containing no lithium. Accepting the idea of explanation the observed properties of lithium in the magnetic chemically peculiar (MCP) stars by the hypothesis of a double (multiple) stellar system with NS companion, it is possible to clarify the evolutionary state of Li-rich, Herbig AeBe, and T Tau type stars and the origin of related stellar groups such as HgMn, AmFm, and δ Scuti type stars.

  13. Surface Treatment of a Lithium Limiter for Spherical Torus Plasma Experiments

    SciTech Connect

    Kaita, R.; Majeski, R.; Doerner, R.; Antar, G.; Timberlake, J.; Spaleta, J.; Hoffman, D.; Jones, B.; Munsat, T.; Kugel, H.; Taylor, G.; Stutman, D.; Soukhanovskii, V.; Maingi, R.; Molesa, S.; Efthimion, P.; Menard, J.; Finkenthal, M.; Luckhardt, S.

    2001-03-20

    The concept of a flowing lithium first wall for a fusion reactor may lead to a significant advance in reactor design, since it could virtually eliminate the concerns with power density and erosion, tritium retention, and cooling associated with solid walls. As part of investigations to determine the feasibility of this approach, plasma interaction questions in a toroidal plasma geometry are being addressed in the Current Drive eXperiment-Upgrade (CDX-U) spherical torus (ST). The first experiments involved a toroidally local lithium limiter (L3). Measurements of pumpout rates indicated that deuterium pumping was greater for the L3 compared to conventional boron carbide limiters. The difference in the pumpout rates between the two limiter types decreased with plasma exposure, but argon glow discharge cleaning was able to restore the pumping effectiveness of the L3. At no point, however, was the extremely low recycling regime reported in previous lithium experiments achieved. This may be due to the much larger lithium surfaces that were exposed to the plasma in the earlier work. The possibility will be studied in the next set of CDX-U experiments, which are to be conducted with a large area, fully toroidal lithium limiter.

  14. Surface Stress during Electro-Oxidation of Carbon Monoxide and Bulk Stress Evolution during Electrochemical Intercalation of Lithium

    NASA Astrophysics Data System (ADS)

    Mickelson, Lawrence

    2011-12-01

    This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two

  15. In situ plasma removal of surface contaminants from ion trap electrodes

    SciTech Connect

    Haltli, Raymond A.

    2015-05-01

    In this thesis, the construction and implementation of an in situ plasma discharge designed to remove surface contaminants from electrodes in an ion trapping experimental system is presented with results. In recent years, many advances have been made in using ion traps for quantum information processing. All of the criteria defined by DiVincenzo for using ion traps for implementing a quantum computer have been individually demonstrated, and in particular surface traps provide a scalable platform for ions. In order to be used for quantum algorithms, trapped ions need to be cooled to their motional (quantum mechanical) ground state. One of the hurdles in integrating surface ion traps for a quantum computer is minimizing electric field noise, which causes the ion to heat out of its motional ground state and which increases with smaller ion-to-electrode distances realized with surface traps. Surface contamination of trap electrodes is speculated to be the primary source of electric field noise. The main goal achieved by this work was to implement an in situ surface cleaning solution for surface electrode ion traps, which would not modify the ion trap electrode surface metal. Care was taken in applying the RF power in order to localize a plasma near the trap electrodes. A method for characterizing the energy of the plasma ions arriving at the ion trap surface is presented and results for plasma ion energies are shown. Finally, a method for quantifying the effectiveness of plasma cleaning of trap electrodes, using the surface analysis technique of X-ray photoelectron spectroscopy for measuring the amount and kind of surface contaminants, is described. A significant advantage of the trap electrode surface cleaning method presented here is the minimal changes necessary for implementation on a working ion trap experimental system.

  16. Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

    PubMed Central

    Doeff, Marca M.; Chen, Guoying; Cabana, Jordi; Richardson, Thomas J.; Mehta, Apurva; Shirpour, Mona; Duncan, Hugues; Kim, Chunjoong; Kam, Kinson C.; Conry, Thomas

    2013-01-01

    Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g. changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g. on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done. PMID:24300777

  17. Characterization of electrode materials for lithium ion and sodium ion batteries using synchrotron radiation techniques.

    PubMed

    Doeff, Marca M; Chen, Guoying; Cabana, Jordi; Richardson, Thomas J; Mehta, Apurva; Shirpour, Mona; Duncan, Hugues; Kim, Chunjoong; Kam, Kinson C; Conry, Thomas

    2013-01-01

    Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g. changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g. on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done. PMID:24300777

  18. Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating.

    PubMed

    Liang, Zheng; Lin, Dingchang; Zhao, Jie; Lu, Zhenda; Liu, Yayuan; Liu, Chong; Lu, Yingying; Wang, Haotian; Yan, Kai; Tao, Xinyong; Cui, Yi

    2016-03-15

    Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium-scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with "lithiophilic" coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm(2) over 80 cycles. PMID:26929378

  19. Photoluminescence excitation of lithium fluoride films by surface plasmon resonance in Kretschmann configuration

    NASA Astrophysics Data System (ADS)

    Bulíř, Jiří; Zikmund, Tomáš; Novotný, Michal; Lančok, Ján; Fekete, Ladislav; Juha, Libor

    2016-04-01

    We report on excitation of the photoluminescence of lithium fluoride by means of the surface plasmon resonance of Al layer. Advantage of this method is high efficiency of the excitation, which is applicable to ultra-thin films. P-polarized UV diode laser light is coupled to the surface plasmon resonance using a fused silica prism in Kretschmann configuration. The angular dependence of the reflected intensity is measured using a theta-2theta goniometer. The surface plasmon at resonance condition induces photoluminescence in the adjacent lithium fluoride layer. The fluoride layers were deposited on Al-coated fused silica substrates by electron beam evaporation. For the experiment, we prepared several samples with thickness ranging from 20 to 71 nm. We studied the effect of the luminescence enhancement by the surface plasmon resonance effect. Strong quenching effect was observed in the thinnest LiF layer. Influence of X-ray irradiation on the photoluminescence was studied.

  20. AC impedance analysis of ionic and electronic conductivities in electrode mixture layers for an all-solid-state lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Siroma, Zyun; Sato, Tomohiro; Takeuchi, Tomonari; Nagai, Ryo; Ota, Akira; Ioroi, Tsutomu

    2016-06-01

    The ionic and electronic effective conductivities of an electrode mixture layers for all-solid-state lithium-ion batteries containing Li2Ssbnd P2S5 as a solid electrolyte were investigated by AC impedance measurements and analysis using a transmission-line model (TLM). Samples containing graphite (graphite electrodes) or LiNi0.5Co0.2Mn0.3O2 (NCM electrodes) as the active material were measured under a "substrate | sample | bulk electrolyte | sample | substrate" configuration (ion-electron connection) and a "substrate | sample | substrate" configuration (electron-electron connection). Theoretically, if the electronic resistance is negligibly small, which is the case with our graphite electrodes, measurement with the ion-electron connection should be effective for evaluating ionic conductivity. However, if the electronic resistance is comparable to the ionic resistance, which is the case with our NCM electrodes, the results with the ion-electron connection may contain some inherent inaccuracy. In this report, we theoretically and practically demonstrate the advantage of analyzing the results with the electron-electron connection, which gives both the ionic and electronic conductivities. The similarity of the behavior of ionic conductivity with the graphite and NCM electrodes confirms the reliability of this analysis.

  1. Synthesis of 2D/2D Structured Mesoporous Co3O4 Nanosheet/N-Doped Reduced Graphene Oxide Composites as a Highly Stable Negative Electrode for Lithium Battery Applications.

    PubMed

    Sennu, Palanichamy; Kim, Hyo Sang; An, Jae Youn; Aravindan, Vanchiappan; Lee, Yun-Sung

    2015-08-01

    Mesoporous Co3O4 nanosheets (Co3 O4 -NS) and nitrogen-doped reduced graphene oxide (N-rGO) are synthesized by a facile hydrothermal approach, and the N-rGO/Co3O4 -NS composite is formulated through an infiltration procedure. Eventually, the obtained composites are subjected to various characterization techniques, such as XRD, Raman spectroscopy, surface area analysis, X-ray photoelectron spectroscopy (XPS), and TEM. The lithium-storage properties of N-rGO/Co3O4 -NS composites are evaluated in a half-cell assembly to ascertain their suitability as a negative electrode for lithium-ion battery applications. The 2D/2D nanostructured mesoporous N-rGO/Co3O4 -NS composite delivered a reversible capacity of about 1305 and 1501 mAh g(-1) at a current density of 80 mA g(-1) for the 1st and 50th cycles, respectively. Furthermore, excellent cyclability, rate capability, and capacity retention characteristics are noted for the N-rGO/Co3O4 -NS composite. This improved performance is mainly related to the existence of mesoporosity and a sheet-like 2D hierarchical morphology, which translates into extra space for lithium storage and a reduced electron pathway. Also, the presence of N-rGO and carbon shells in Co3O4 -NS should not be excluded from such exceptional performance, which serves as a reliable conductive channel for electrons and act as synergistically to accommodate volume expansion upon redox reactions. Ex-situ TEM, impedance spectroscopy, and XPS, are also conducted to corroborate the significance of the 2D morphology towards sustained lithium storage. PMID:26033848

  2. Design and simulation of lithium rechargeable batteries

    SciTech Connect

    Doyle, C.M.

    1995-08-01

    Lithium -based rechargeable batteries that utilize insertion electrodes are being considered for electric-vehicle applications because of their high energy density and inherent reversibility. General mathematical models are developed that apply to a wide range of lithium-based systems, including the recently commercialized lithium-ion cell. The modeling approach is macroscopic, using porous electrode theory to treat the composite insertion electrodes and concentrated solution theory to describe the transport processes in the solution phase. The insertion process itself is treated with a charge-transfer process at the surface obeying Butler-Volmer kinetics, followed by diffusion of the lithium ion into the host structure. These models are used to explore the phenomena that occur inside of lithium cells under conditions of discharge, charge, and during periods of relaxation. Also, in order to understand the phenomena that limit the high-rate discharge of these systems, we focus on the modeling of a particular system with well-characterized material properties and system parameters. The system chosen is a lithium-ion cell produced by Bellcore in Red Bank, NJ, consisting of a lithium-carbon negative electrode, a plasticized polymer electrolyte, and a lithium-manganese-oxide spinel positive electrode. This battery is being marketed for consumer electronic applications. The system is characterized experimentally in terms of its transport and thermodynamic properties, followed by detailed comparisons of simulation results with experimental discharge curves. Next, the optimization of this system for particular applications is explored based on Ragone plots of the specific energy versus average specific power provided by various designs.

  3. Power spectra and autocorrelation functions for surface diffusion of lithium on tungsten

    NASA Astrophysics Data System (ADS)

    Gładyszewski, L.

    1989-04-01

    The surface ionization of lithium on polycrystalline tungsten and ionic thermal desorption are studied by a method based on the Li + ion current noise arising from the fluctuation of the work function as a result of random fluctuations of the Li adsorbate density. The activation energy for surface diffusion and energy of desorption for Li atoms have been determined by measuring the time correlation function of the local ion thermoemission current fluctuations.

  4. Negative electrode composition

    DOEpatents

    Kaun, Thomas D.; Chilenskas, Albert A.

    1982-01-01

    A secondary electrochemical cell and a negative electrode composition for use therewith comprising a positive electrode containing an active material of a chalcogen or a transiton metal chalcogenide, a negative electrode containing a lithium-aluminum alloy and an amount of a ternary alloy sufficient to provide at least about 5 percent overcharge capacity relative to a negative electrode solely of the lithium-aluminum alloy, the ternary alloy comprising lithium, aluminum, and iron or cobalt, and an electrolyte containing lithium ions in contact with both of the positive and the negative electrodes. The ternary alloy is present in the electrode in the range of from about 5 percent to about 50 percent by weight of the electrode composition and may include lithium-aluminum-nickel alloy in combination with either the ternary iron or cobalt alloys. A plurality of series connected cells having overcharge capacity can be equalized on the discharge side without expensive electrical equipment.

  5. 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.

  6. 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

    2014-01-01

    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. PMID:24670975

  7. Synthesis and electrochemical performance of surface-modified nano-sized core/shell tin particles for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Schmuelling, Guido; Oehl, Nikolas; Knipper, Martin; Kolny-Olesiak, Joanna; Plaggenborg, Thorsten; Meyer, Hinrich-Wilhelm; Placke, Tobias; Parisi, Jürgen; Winter, Martin

    2014-09-01

    Tin is able to lithiate and delithiate reversibly with a high theoretical specific capacity, which makes it a promising candidate to supersede graphite as the state-of-the-art negative electrode material in lithium ion battery technology. Nevertheless, it still suffers from poor cycling stability and high irreversible capacities. In this contribution, we show the synthesis of three different nano-sized core/shell-type particles with crystalline tin cores and different amorphous surface shells consisting of SnOx and organic polymers. The spherical size and the surface shell can be tailored by adjusting the synthesis temperature and the polymer reagents in the synthesis, respectively. We determine the influence of the surface modifications with respect to the electrochemical performance and characterize the morphology, structure, and thermal properties of the nano-sized tin particles by means of high-resolution transmission electron microscopy, x-ray diffraction, and thermogravimetric analysis. The electrochemical performance is investigated by constant current charge/discharge cycling as well as cyclic voltammetry.

  8. Effects of electrode surface roughness on motional heating of trapped ions

    NASA Astrophysics Data System (ADS)

    Lin, Kuan-Yu; Low, Guang Hao; Chuang, Isaac L.

    2016-07-01

    Electric-field noise is a major source of motional heating in trapped-ion quantum computation. While the influence of trap-electrode geometries on electric-field noise has been studied in patch potential and surface adsorbate models, only smooth surfaces are accounted for by current theory. The effects of roughness, a ubiquitous feature of surface electrodes, are poorly understood. We investigate its impact on electric-field noise by deriving a rough-surface Green's function and evaluating its effects on adsorbate-surface binding energies. At cryogenic temperatures, heating-rate contributions from adsorbates are predicted to exhibit an exponential sensitivity to local surface curvature, leading to either a large net enhancement or suppression over smooth surfaces. For typical experimental parameters, orders-of-magnitude variations in total heating rates can occur depending on the spatial distribution of adsorbates. Through careful engineering of electrode surface profiles, our results suggests that heating rates can be tuned over orders of magnitudes.

  9. Surface defects on n-MoSe2 electrodes used in photoelectrochemical solar cells

    NASA Astrophysics Data System (ADS)

    Peraldo Bicelli, L.; Razzini, G.

    1983-12-01

    It is pointed out that stable and efficient electrochemical solar cells based on layered semiconducting materials have been obtained with single-crystal electrodes. It is necessary that the electrode materials have a very high degree of crystalline perfection, while the active surface of the electrode must be parallel to the van der Waals plane. The present investigation is concerned with two problems, taking into account the influence of local variations in the stoichiometric composition of the electrode material on the performance, and the photocatalytic process occurring on the active areas of the electrode. The obtained results provide information concerning the problems which have to be solved to obtain transition metal dichalcogenide electrodes for solid-liquid junction cells with an photoelectrochemical behavior suitable for practical applications.

  10. Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

    NASA Astrophysics Data System (ADS)

    Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

    Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

  11. Retention/Diffusivity Studies in Free-Surface Flowing Liquid Lithium

    SciTech Connect

    R.A. Stubbers; G.H. Miley; M. Nieto; W. Olczak; D.N. Ruzic; A. Hassanein

    2004-12-14

    FLIRE was designed to measure the hydrogen and helium retention and diffusivity in a flowing stream of liquid lithium, and it has accomplished these goals. Retention coefficients for helium in the flowing liquid stream were 0.1-2% for flow speeds of 44 cm/s and implantation energies between 500 and 2000 eV. The energy dependence of retention is linear for the energy range considered, as expected, and the dependence of retention on flow velocity fits the expected square-root of flow speed dependence. Estimates of the helium diffusion coefficient in the flowing lithium stream were {approx} 4 x 10{sup -7} cm{sup 2}/s, and are independent of implantation energy. This value is much lower than expected, which could be due to several factors, such as mixing, bubble formation or surface film formation. In the case of hydrogen, long term retention and release mechanisms are of greatest importance, since this relates to tritium inventory in flowing lithium PFCs for fusion applications. The amount of hydride formation was measured for flowing lithium exposed to neutral deuterium gas. Thermal desorption spectroscopy (TDS) measurements indicate that the hydride concentration was between 0.1 and 0.2% over a wide range of pressures (6.5 x 10{sup -5} to 1 Torr). This result implies that the deuterium absorption rate is limited by the surface dissociation rate, since deuterium (hydrogen/tritium) is absorbed in its atomic form, not its molecular form.

  12. Understanding sodium versus lithium intercalation potentials of electrode materials for alkali-ion batteries

    NASA Astrophysics Data System (ADS)

    Arroyo-de Dompablo, M. Elena

    2014-08-01

    Differences in average voltages for the alkali ion intercalation (Li, Na) in a variety of electrode materials are investigated. The average Li and Na insertion potentials in the cavities of ◻ReO3-perovskite, ramsdellite-◻Ti2O4, layered-◻2A2Ti3O7 (A = Li, Na) and NASICON-◻Na3Ti2(PO4)3 have been calculated by first principles calculations at the density functional theory level. The results identify the type of site occupied by the inserted ion as the relevant structural parameter. Occupation of large sites (c.n. = 12, 8) might yield Na insertion voltages higher than Li ones. On the other extreme, occupation of tetrahedral sites raises the Li insertion voltage as much as 0.8 V above the Na one. For octahedral sites the higher polarizing character of Li ions vs. Na ions acts as a key-factor to bring the Li intercalation voltage above that of Na intercalation.

  13. Mesoscale Phase-Field Modeling of Charge Transport in Nanocomposite Electrodes for Lithium-ion Batteries

    SciTech Connect

    Hu, Shenyang Y.; Li, Yulan; Rosso, Kevin M.; Sushko, Maria L.

    2013-01-10

    A phase-field model is developed to investigate the influence of microstructure, thermodynamic and kinetic properties, and charging conditions on charged particle transport in nanocomposite electrodes. Two sets of field variables are used to describe the microstructure. One is comprised of the order parameters describing size, orientation and spatial distributions of nanoparticles, and the other is comprised of the concentrations of mobile species. A porous nanoparticle microstructure filled with electrolyte is taken as a model system to test the phase-field model. Inhomogeneous and anisotropic dielectric constants and mobilities of charged particles, and stresses associated with lattice deformation due to Li-ion insertion/extraction are considered in the model. Iteration methods are used to find the elastic and electric fields in an elastically and electrically inhomogeneous medium. The results demonstrate that the model is capable of predicting charge separation associated with the formation of a double layer at the electrochemical interface between solid and electrolyte, and the effect of microstructure, inhomogeneous and anisotropic thermodynamic and kinetic properties, charge rates, and stresses on voltage versus current density and capacity during charging and discharging.

  14. Simulating Supercapacitors: Can We Model Electrodes As Constant Charge Surfaces?

    PubMed

    Merlet, Céline; Péan, Clarisse; Rotenberg, Benjamin; Madden, Paul A; Simon, Patrice; Salanne, Mathieu

    2013-01-17

    Supercapacitors based on an ionic liquid electrolyte and graphite or nanoporous carbon electrodes are simulated using molecular dynamics. We compare a simplified electrode model in which a constant, uniform charge is assigned to each carbon atom with a realistic model in which a constant potential is applied between the electrodes (the carbon charges are allowed to fluctuate). We show that the simulations performed with the simplified model do not provide a correct description of the properties of the system. First, the structure of the adsorbed electrolyte is partly modified. Second, dramatic differences are observed for the dynamics of the system during transient regimes. In particular, upon application of a constant applied potential difference, the increase in the temperature, due to the Joule effect, associated with the creation of an electric current across the cell follows Ohm's law, while unphysically high temperatures are rapidly observed when constant charges are assigned to each carbon atom. PMID:26283432

  15. Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode

    PubMed Central

    David, L.; Bhandavat, R.; Barrera, U.; Singh, G.

    2015-01-01

    A facile process is demonstrated for the synthesis of layered SiCN-MoS2 structure via pyrolysis of polysilazane functionalized MoS2 flakes. The layered morphology and polymer to ceramic transformation on MoS2 surfaces was confirmed by use of electron microscopy and spectroscopic techniques. Tested as thick film electrode in a Li-ion battery half-cell, SiCN-MoS2 showed the classical three-stage reaction with improved cycling stability and capacity retention than neat MoS2. Contribution of conversion reaction of Li/MoS2 system on overall capacity was marginally affected by the presence of SiCN while Li-irreversibility arising from electrolyte decomposition was greatly suppressed. This is understood as one of the reasons for decreased first cycle loss and increased capacity retention. SiCN-MoS2 in the form of self-supporting paper electrode (at 6 mg·cm−2) exhibited even better performance, regaining initial charge capacity of approximately 530 mAh·g−1 when the current density returned to 100 mA·g−1 after continuous cycling at 2400 mA·g−1 (192 mAh·g−1). MoS2 cycled electrode showed mud-cracks and film delamination whereas SiCN-MoS2 electrodes were intact and covered with a uniform solid electrolyte interphase coating. Taken together, our results suggest that molecular level interfacing with precursor–derived SiCN is an effective strategy for suppressing the metal-sulfide/electrolyte degradation reaction at low discharge potentials. PMID:25851595

  16. Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode

    NASA Astrophysics Data System (ADS)

    David, L.; Bhandavat, R.; Barrera, U.; Singh, G.

    2015-04-01

    A facile process is demonstrated for the synthesis of layered SiCN-MoS2 structure via pyrolysis of polysilazane functionalized MoS2 flakes. The layered morphology and polymer to ceramic transformation on MoS2 surfaces was confirmed by use of electron microscopy and spectroscopic techniques. Tested as thick film electrode in a Li-ion battery half-cell, SiCN-MoS2 showed the classical three-stage reaction with improved cycling stability and capacity retention than neat MoS2. Contribution of conversion reaction of Li/MoS2 system on overall capacity was marginally affected by the presence of SiCN while Li-irreversibility arising from electrolyte decomposition was greatly suppressed. This is understood as one of the reasons for decreased first cycle loss and increased capacity retention. SiCN-MoS2 in the form of self-supporting paper electrode (at 6 mg.cm-2) exhibited even better performance, regaining initial charge capacity of approximately 530 mAh.g-1 when the current density returned to 100 mA.g-1 after continuous cycling at 2400 mA.g-1 (192 mAh.g-1). MoS2 cycled electrode showed mud-cracks and film delamination whereas SiCN-MoS2 electrodes were intact and covered with a uniform solid electrolyte interphase coating. Taken together, our results suggest that molecular level interfacing with precursor-derived SiCN is an effective strategy for suppressing the metal-sulfide/electrolyte degradation reaction at low discharge potentials.

  17. Silver nanowire/polyaniline composite transparent electrode with improved surface properties

    SciTech Connect

    Kumar, A.B.V. Kiran; Jiang, Jianwei; Bae, Chang Wan; Seo, Dong Min; Piao, Longhai Kim, Sang-Ho

    2014-09-15

    Highlights: • AgNWs/PANI transparent electrode was prepared by layer-by-layer coating method. • The surface roughness of the electrode reached to 6.5 nm (root mean square). • The electrode had reasonable sheet resistance (25 Ω/□) and transmittance (83.5%). - Abstract: Silver nanowires (AgNWs) are as potential candidates to replace indium tin oxide (ITO) in transparent electrodes because of their preferred conducting and optical properties. However, their rough surface properties are not favorable for the fabrication of optoelectronic devices, such as displays and thin-film solar cells. In the present investigation, AgNWs/polyaniline composite transparent electrodes with better surface properties were successfully prepared. AgNWs were incorporated into polyaniline:polystyrene sulfonate (PANI:PSS) by layer-by-layer coating and mechanical pressing. PANI:PSS decreased the surface roughness of the AgNWs electrode by filling the gap of the random AgNWs network. The transparent composite electrode had decreased surface roughness (root mean square 6.5 nm) with reasonable sheet resistance (25 Ω/□) and transmittance (83.5%)

  18. Favorable combination of positive and negative electrode materials with glyme-Li salt complex electrolytes in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Orita, A.; Kamijima, K.; Yoshida, M.; Dokko, K.; Watanabe, M.

    Tetraglyme (G4)-lithium bis(trifluoromethanesulfonyl)amide (TFSA) complexes with different G4 ratio were investigated. An increase in the amount of G4 led to the decrease in the viscosity, and increase in the ionic conductivity of the complex, and G4-LiTFSA showed higher thermal stabilities than the conventional organic electrolyte, when the molar ratio of G4 was more than 40 mol%. The increase in the G4 amount improved the rate capabilities of Li/LiCoO 2 cells in the range where the molar ratio of G4 was between 40 mol% and 60 mol%. The stable Li ion intercalation-deintercalation was not observed in the Li/graphite cell of [Li(G4)][TFSA] (G4: 50 mol%) without additives. However, the additives for forming solid electrolyte interface (SEI) film, such as vinylene carbonate, vinylethylene carbonate, and 1,3-propane sultone, led to the charge-discharge performance comparable to that of the conventional organic electrolyte. The adoption of Li 4Ti 5O 12 and LiFePO 4 led to excellent reversibilities of the Li half cells using [Li(G4)][TFSA], probably because of the favorable operation voltage. In the case of the LiFePO 4/Li 4Ti 5O 12 cell, the cell with [Li(G4)][TFSA] showed the better rate capability than that with the conventional organic electrolyte, when the rate was less than 1 CmA, and it is concluded that [Li(G4)][TFSA] can be the candidate as the alternative of organic electrolytes when the most appropriate electrode-active materials are used.

  19. in situ plasma removal of surface contaminants from ion trap electrodes

    SciTech Connect

    Haltli, Raymond A.

    2015-04-01

    This research resulted in a construction and implementation of an in situ plasma discharge to remove surface contaminants from electrodes in an ion trapping experimental system is presented with results.

  20. Analysis of effects of the state of charge on the formation and growth of the deposit layer on graphite electrode of pouch type lithium ion polymer batteries

    NASA Astrophysics Data System (ADS)

    Agubra, Victor A.; Fergus, Jeffrey W.; Fu, Rujian; Choe, Song-Yul

    2014-12-01

    The breakdown of the protective solid electrolyte interface (SEI) layer formed on lithium ion battery anodes can initiate further electrolyte decomposition and the formation of non-uniform and electronically insulating reaction products on the surface of the graphite particles. The results from this study indicate that raising both the lower and upper ends of the state of charge (SOC) increased the rate of the electrolyte decomposition side reaction to form a thick deposit surface film. This deposit layer contained lithium that can no longer participate in the reversible electrochemical reaction. In addition, the high cycling potential coupled with high charge rate created a large lithium concentration gradient that led to some particles detachment from the current collector and isolation in the electrochemical process.