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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. Surface stabilized electrodes for lithium batteries

    SciTech Connect

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

    2015-09-08

    A stabilized electrode comprising a metal oxide or lithium-metal-oxide electrode material is formed by contacting a surface of the electrode material, prior to cell assembly, with an aqueous or a non-aqueous acid solution having a pH greater than 4 but less than 7 and containing a stabilizing salt, to etch the surface of the electrode material and introduce stabilizing anions and cations from the salt into said surface. The structure of the bulk of the electrode material remains unchanged during the acid treatment. The stabilizing salt comprises fluoride and at least one cationic material selected from the group consisting of ammonium, phosphorus, titanium, silicon, zirconium, aluminum, and boron.

  3. 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.

  4. Surface modifications of electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Fu, L. J.; Liu, H.; Li, C.; Wu, Y. P.; Rahm, E.; Holze, R.; Wu, H. Q.

    2006-02-01

    Since the birth of the lithium ion battery in the early 1990s, its development has been very rapid and it has been widely applied as power source for a lot of light and high value electronics due to its significant advantages over traditional rechargeable battery systems. Recent research demonstrates the importance of surface structural features of electrode materials for their electrochemical performance, and in this paper the latest progress on this aspect is reviewed. Electrode materials are either anodic or cathodic ones. The former mainly include graphitic carbons, whose surfaces can be modified by mild oxidation, deposition of metals and metal oxides, coating with polymers and other kinds of carbons. Through these modifications, the surface structures of the graphitic carbon anodes are improved, and these improvements include: (1) smoothing the active edge surfaces by removing some reactive sites and/or defects on the graphite surface, (2) forming a dense oxide layer on the graphite surface, and (3) covering active edge structures on the graphite surface. Meanwhile, other accompanying changes occur: (1) production of nanochannels/micropores, (2) an increase in the electronic conductivity, (3) an inhibition of structural changes during cycling, (4) a reduction of the thickness of the SEI (solid-electrolyte-interface) layer, and (5) an increase in the number of host sites for lithium storage. As a result, the direct contact of graphite with the electrolyte solution is prevented, its surface reactivity with electrolytes, the decomposition of electrolytes, the co-intercalation of the solvated lithium ions and the charge-transfer resistance are decreased, and the movement of graphene sheets is inhibited. When the surfaces of cathode materials, mainly including LiCoO 2, LiNiO 2 and LiMn 2O 4, are coated with oxides such as MgO, Al 2O 3, ZnO, SnO 2, ZrO 2, Li 2Oṡ2B 2O 3 glass and other electroactive oxides, the coating can prevent their direct contact with the

  5. In situ Raman spectroscopy of lithium electrode surface in ambient temperature lithium secondary battery. Final report

    SciTech Connect

    Tachikawa, Hiroyasu

    1992-09-01

    Raman spectroscopy was used to characterize surface layers on lithium electrodes in different solvents such as propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and polyethylene glycol 400 dimethyl ether (PEG400DME). Both DMC and DEC were used singly, and also mixed with either methyl acetate (MA) or methyl formate (MF). The Raman spectra showed that passive films formed on the Li surface in different solvents may have different chemical structures, which changed during the charging and discharging processes. Raman spectroscopy was also applied to characterize zinc electrode surfaces in alkaline solutions. The results suggested that ZnO and Zn(OH){sub 2} formed on the Zn electrode when a passive potential was applied. A solid film of fullerene C{sub 60}, which could be used as a cathode in Li rechargeable batteries, was examined in the PEG400DME solution by both electrochemical and Raman spectroscopy. Cyclic voltammograms (CVs) showed five redox peaks which suggested the formation of C{sub 60}{sup {minus}}, C{sub 60}{sup 2{minus}}, C{sub 60}{sup 3{minus}}, C{sub 60}{sup 4{minus}}, and C{sub 60}{sup 5{minus}}. Raman spectra obtained from a thin C{sub 60} film indicated that the thin fulleride film dissolved in the PEG400DME/LiClO{sub 4} solution at negative potentials.

  6. 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.

  7. Molecular Layer Deposition for Surface Modification of Lithium-Ion Battery Electrodes

    SciTech Connect

    Ban, Chunmei; George, Steven M.

    2016-10-21

    Inspired by recent successes in applying molecular layer deposition (MLD) to stabilize lithium-ion (Li-ion) electrodes, this review presents the MLD process and its outstanding attributes for electrochemical applications. The review discusses various MLD materials and their implementation in Li-ion electrodes. The rationale behind these emerging uses of MLD is examined to motivate future efforts on the fundamental understanding of interphase chemistry and the development of new materials for enhanced electrochemical performance.

  8. 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.

  9. 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.

  10. Conductive lithium storage electrode

    DOEpatents

    Chiang, Yet-Ming [Framingham, MA; Chung, Sung-Yoon [Incheon, KR; Bloking, Jason T [Mountain View, CA; Andersson, Anna M [Vasteras, SE

    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.

  11. 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.

  12. Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Jung, Sung-Kyun; Kim, Hyunchul; Cho, Min Gee; Cho, Sung-Pyo; Lee, Byungju; Kim, Hyungsub; Park, Young-Uk; Hong, Jihyun; Park, Kyu-Young; Yoon, Gabin; Seong, Won Mo; Cho, Yongbeom; Oh, Myoung Hwan; Kim, Haegyeom; Gwon, Hyeokjo; Hwang, Insang; Hyeon, Taeghwan; Yoon, Won-Sub; Kang, Kisuk

    2017-01-01

    Lithium-ion batteries based on intercalation compounds have dominated the advanced portable energy storage market. The positive electrode materials in these batteries belong to a material group of lithium-conducting crystals that contain redox-active transition metal and lithium. Materials without lithium-conducting paths or lithium-free compounds could be rarely used as positive electrodes due to the incapability of reversible lithium intercalation or the necessity of using metallic lithium as negative electrodes. These constraints have significantly limited the choice of materials and retarded the development of new positive electrodes in lithium-ion batteries. Here, we demonstrate that lithium-free transition metal monoxides that do not contain lithium-conducting paths in their crystal structure can be converted into high-capacity positive electrodes in the electrochemical cell by initially decorating the monoxide surface with nanosized lithium fluoride. This unusual electrochemical behaviour is attributed to a surface conversion reaction mechanism in contrast with the classic lithium intercalation reaction. Our findings will offer a potential new path in the design of positive electrode materials in lithium-ion batteries.

  13. Positive electrode for a lithium battery

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2015-04-07

    A method for producing a lithium alkali transition metal oxide for use as a positive electrode material for lithium secondary batteries by a precipitation method. The positive electrode material is a lithium alkali transition metal composite oxide and is prepared by mixing a solid state mixed with alkali and transition metal carbonate and a lithium source. The mixture is thermally treated to obtain a small amount of alkali metal residual in the lithium transition metal composite oxide cathode material.

  14. Ionic transport in passivation layered on the lithium electrode

    NASA Astrophysics Data System (ADS)

    Nimon, Eugeny S.; Churikov, Alexei V.; Shirokov, Alexander V.; Lvov, Arlen L.; Chuvashkin, Anatoly N.

    1993-04-01

    The processes of ionic transport in passivating layers on the surface of the lithium electrode in solutions based on thionyl chloride, propylene carbonate and gamma -butyrolactone have been studied by means of pulse electrochemical methods. The data obtained are quantitatively described by a model which takes into account transport of both the intrinsic mobile lithium ions of the passivating layer and lithium ions injected into the passivating layer from the electrode or from the electrolyte solution under anodic or cathodic current directions, respectively. The values of mobility and concentration of mobile lithium ions in passivating layers formed on lithium in various solutions under open-circuit conditions have been determined.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Electrode Nanostructures in Lithium-Based Batteries.

    PubMed

    Mahmood, Nasir; Hou, Yanglong

    2014-12-01

    Lithium-based batteries possessing energy densities much higher than those of the conventional batteries belong to the most promising class of future energy devices. However, there are some fundamental issues related to their electrodes which are big roadblocks in their applications to electric vehicles (EVs). Nanochemistry has advantageous roles to overcome these problems by defining new nanostructures of electrode materials. This review article will highlight the challenges associated with these chemistries both to bring high performance and longevity upon considering the working principles of the various types of lithium-based (Li-ion, Li-air and Li-S) batteries. Further, the review discusses the advantages and challenges of nanomaterials in nanostructured electrodes of lithium-based batteries, concerns with lithium metal anode and the recent advancement in electrode nanostructures.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Enhanced Lithium-Ion Intercalation Properties of V[subscript 2]O[subscript 5] Xerogel Electrodes with Surface Defects

    SciTech Connect

    Liu, Dawei; Liu, Yanyi; Pan, Anquiang; Nagle, Kenneth P.; Seidler, Gerald T.; Jeong, Yoon-Ha; Cao, Guozhong

    2011-09-15

    V{sub 2}O{sub 5} xerogel films were fabricated by casting V{sub 2}O{sub 5} sols onto fluorine-doped tin oxide (FTO) glass substrates and annealing at 300 C for 3 h in different annealing atmospheres of air and nitrogen. Films prepared in different annealing conditions possess different grain sizes and crystallinity, while the vanadium ion oxidation state also varies, as identified by X-ray absorption spectroscopy. A nitrogen annealing atmosphere induces the presence of defects, such as V{sup 4+} ions, and associated oxygen vacancies. Thus, the presence of defects, whether on the film surface or in the bulk, can be controlled by using air and nitrogen annealing atmospheres in the proper order. Electrochemical impedance analyses reveal enhanced charge-transfer conductivity in films with more V{sup 4+} and oxygen vacancies on the film surface, that is, a film annealed, first, for 0.5 h in air and then for 2.5 h in nitrogen. Lithium-ion intercalation measurements show that, at a charge/discharge current density of 600 mA g{sup -1}, this film possesses a noticeably better lithium-ion storage capability than films without surface defects. This sample starts with an initial discharge capacity of 139 mA h g{sup -1}, and the capacity increases slowly to a maximum value of 156 mA h g{sup -1} in the 15th cycle, followed by a mild capacity degradation in later cycles. After 50 cycles, the discharge capacity is still as high as 136 mA h g{sup -1}. A much improved lithium-ion intercalation capacity and cyclic stability are attributed to V{sup 4+} surface defects and associated oxygen vacancies introduced by N{sub 2} annealing.

  9. Relationship between surface chemistry and electrochemical behavior of LiNi1/2Mn1/2O2 positive electrode in a lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Dupré, Nicolas; Martin, Jean-Frédéric; Oliveri, Julie; Soudan, Patrick; Yamada, Atsuo; Kanno, Ryoji; Guyomard, Dominique

    2011-05-01

    The formation and the evolution of lithium-containing species on the surface of grains of a layered 4 V material such as LiNi1/2Mn1/2O2 along the electrochemical cycling have been followed using 7Li MAS NMR, electrochemical impedance spectroscopy (EIS) and XPS. Materials displaying different specific surface areas and stored in different atmospheres have been investigated in order to study the influence of the surface/volume ratio and the influence of the initial surface state, respectively. It is shown that the presence of an initial interphase of Li2CO3 influences the electrochemical behavior of the electrode, emphasizing the importance of the history of the electrode prior cycling. 7Li MAS NMR experiments performed upon cycling indicate the formation of interphase species in reduction and their partial removal in oxidation, indicating the dynamic character of the interphase upon cycling. Combined NMR, EIS and XPS experiments show the strong influence of the electrode/electrolyte interphase evolution on the electrochemical performance. Such results lead us to draw conclusions on the optimal storage conditions of layered 4 V materials for Li-ion batteries such as LiNi1/2Mn1/2O2.

  10. 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.

  11. 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.

  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. 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.

  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. 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.

  2. 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.

  3. 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

  4. 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.

  5. Poly(acetylene) as a positive electrode in lithium sulfur oxyhalide cells

    NASA Astrophysics Data System (ADS)

    Calvert, Jeffrey M.; Weiner, Bryndyn; Smith, Jerry J.; Nowak, Robert J.

    1989-03-01

    Conductive poly(acetylene) film was employed as the positive electrode in primary lithium/thionyl chloride and lithium/sulfuryl chloride cells. Neutral (CH)x, doped to the metallic state upon in situ exposure to LiAlCl4/sulfur oxyhalide electrolytes, acts as a catalytic surface rather than as the active electrochemical element. Sulfur oxyhalides were reduced on(CH)x film at high rates as on PTFE-bonded Shawinigan carbon black felt. Electrode capacity was limited by the inability of the electrolyte to permeate the (CH)x film and the formation of a surface passive filmby discharge products.

  6. 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.

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

    DOEpatents

    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.

  8. 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.

  9. 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.

  10. 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.

  11. Electrode structures and surfaces for Li batteries

    DOEpatents

    Thackeray, Michael M.; Kang, Sun-Ho; Balasubramanian, Mahalingam; Croy, Jason

    2017-03-14

    This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.

  12. 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.

  13. Development of Novel Metal Hydride-Carbon Nanomaterial Based Nanocomposites as Anode Electrode Materials for Lithium Ion Battery

    DTIC Science & Technology

    2014-06-30

    and pG-f-MWNT after the first cycle. These may be attributed to the lithium ion consumption during the electrolyte decomposition and formation of... solid electrolyte interface film around the electrodes with large surface areas.25 After the 30th and the 100th cycle SEG yielded a reversible discharge...anode electrode materials for Lithium ion battery Objectives:- The aim of this study is to develop metal hydride–carbon nanomaterial based

  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. Phase transitions in insertion electrodes for lithium batteries

    SciTech Connect

    Thackeray, M. M.

    2000-02-02

    Phase transitions that occur during lithium insertion into layered and framework structures are discussed in the context of their application as positive and negative electrodes in lithium-ion batteries. The discussion is focused on the two-dimensional structures of graphite, LiNi{sub 1{minus}x}M{sub x}O{sub 2} (M = Co, Ti and Mg), and Li{sub 1.2}V{sub 3}O{sub 8}; examples of framework structures with a three-dimensional interstitial space for Li{sup +}-ion transport include the spinel oxides and intermetallic compounds with zinc-blende-type structures. The phase transitions are discussed in terms of their tolerance to lithium insertion and extraction and to the chemical stability of the electrodes in the cell environment.

  16. Organometallic-inorganic hybrid electrodes for lithium-ion batteries

    DOEpatents

    Huang, Qian; Lemmon, John P.; Choi, Daiwon; Cosimbescu, Lelia

    2016-09-13

    Disclosed are embodiments of active materials for organometallic and organometallic-inorganic hybrid electrodes and particularly active materials for organometallic and organometallic-inorganic hybrid cathodes for lithium-ion batteries. In certain embodiments the organometallic material comprises a ferrocene polymer.

  17. Polarization of the lithium electrode in sulfuryl chloride solutions

    NASA Astrophysics Data System (ADS)

    Alessandrini, F.; Scrosati, B.; Croce, F.; Lazzari, M.; Bonino, F.

    1983-05-01

    The growth of the passivating film on a lithium electrode in contact with sulfuryl chloride solutions has been examined by micropolarization and complex impedance measurements. The results tend to confirm the hypothesis of a two-layer film, where probably the first layer is thin and compact and the second layer is porous and defective.

  18. 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.

  19. 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

    2016-06-14

    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.

  20. 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.

  1. 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

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

    DOEpatents

    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.

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

    DOEpatents

    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.

  4. Aqueous processing of composite lithium ion electrode material

    DOEpatents

    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.

  5. Polysiloxane binder for lithium ion battery electrodes

    DOEpatents

    Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

    2015-10-13

    An electrode includes a binder and an electroactive material, wherein the binder includes a polymer including a linear polysiloxane or a cyclic polysiloxane. The polymer may be generally represented by Formula I: ##STR00001##

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. Lithium ion phase-transfer reaction at the interface between the lithium manganese oxide electrode and the nonaqueous electrolyte.

    PubMed

    Kobayashi, Shota; Uchimoto, Yoshiharu

    2005-07-14

    The lithium ion phase-transfer reaction between the spinel lithium manganese oxide electrode and a nonaqueous electrolyte was investigated by the ac impedance spectroscopic method. The dependence of the impedance spectra on the electrochemical potential of the lithium ion in the electrode, the lithium salt concentration in the electrolyte, the kind of solvent, and the measured temperature were examined. Nyquist plots, obtained from the impedance measurements, consist of two semicircles for high and medium frequency and warburg impedance for low frequency, indicating that the reaction process of two main steps for high and medium frequency obey the Butler-Volmer type equation and could be related to the charge-transfer reaction process accompanied with lithium ion phase-transfer at the interface. The dependency on the solvent suggests that both steps in the lithium ion phase-transfer at the electrode/electrolyte interface include the desolvation process and have high activation barriers.

  11. XPS analysis of lithium surface and modification of surface state for uniform deposition of lithium

    SciTech Connect

    Kanamura, K.; Shiraishi, S.; Takehara, Z.

    1995-12-31

    The surface modification of lithium deposited at various current densities in propylene carbonate containing 1.0 ml dm{sup {minus}3} LiClO{sub 4} was performed by addition of various amounts of HF into the electrolyte, in order to investigate the effect of the HF addition on the surface reaction of lithium. XPS and SEM analyses showed that the surface state of lithium was influenced by the concentration of HF and the electrodeposition current. These two parameters are related to the chemical reaction rate of the lithium surface with HF and the electrodeposition rate of lithium, respectively. The surface modification was highly effective in suppressing lithium dendrite formation when the chemical reaction rate with HF was greater than the electrochemical deposition rate of lithium.

  12. 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.

  13. 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.

  14. High performance lithium insertion negative electrode materials for electrochemical devices

    NASA Astrophysics Data System (ADS)

    Channu, V. S. Reddy; Rambabu, B.; Kumari, Kusum; Kalluru, Rajmohan R.; Holze, Rudolf

    2016-11-01

    Spinel LiCrTiO4 oxides to be used as electrode materials for a lithium ion battery and an asymmetric supercapacitor were synthesized using a soft-chemical method with and without chelating agents followed by calcination at 700 °C for 10 h. Structural and morphological properties were studied with powder X-ray diffraction, scanning electron and transmission electron microscopy. Particles of 50-10 nm in size are observed in the microscopic images. The presence of Cr and Ti is confirmed from the EDS spectrum. Electrochemical properties of LiCrTiO4 electrode were examined in a lithium ion battery. The electrode prepared with oxalic acid-assisted LiCrTiO4 shows higher specific capacity.This LiCrTiO4 is also used as anode material for an asymmetric hybrid supercapacitor. The cell exhibits a specific capacity of 65 mAh/g at 1 mA/cm2. The specific capacity decreases with increasing current densities.

  15. A density functional theory study of the carbon-coating effects on lithium iron borate battery electrodes.

    PubMed

    Loftager, Simon; García-Lastra, Juan María; Vegge, Tejs

    2017-01-18

    Lithium iron borate (LiFeBO3) is a promising cathode material due to its high theoretical specific capacity, inexpensive components and small volume change during operation. Yet, challenges related to severe air- and moisture-induced degradation have prompted the utilization of a protective coating on the electrode which also improves the electronic conductivity. However, not much is known about the preferential geometries of the coating as well as how these coating-electrode interfaces influence the lithium diffusion between the coating and the electrode. Here, we therefore present a density functional theory (DFT) study of the anchoring configurations of carbon coating on the LiFeBO3 electrode and its implications on the interfacial lithium diffusion. Due to large barriers associated with Li-ion diffusion through a parallel-oriented pristine graphene coating on the FeBO3 and LiFeBO3 electrode surfaces, large structural defects in the graphene coating are required for fast Li-ion diffusion. However, such defects are expected to exist only in small concentrations due to their high formation energies. Alternative coating geometries were therefore investigated, and the configuration in which the coating layers were anchored normal to the electrode surface at B and O atoms was found to be most stable. Nudged elastic band (NEB) calculations of the lithium diffusion barriers across the interface between the optimally oriented coating layers and the electrode show no kinetic limitations for lithium extraction and insertion. Additionally, this graphite-coating configuration showed partial blocking of electrode-degrading species.

  16. TiO2/graphene sandwich paper as an anisotropic electrode for high rate lithium ion batteries.

    PubMed

    Li, Na; Zhou, Guangmin; Fang, Ruopian; Li, Feng; Cheng, Hui-Ming

    2013-09-07

    We designed an anisotropic electrode, in which Li(+) ion insertion and diffusion are anisotropic, by controlled growth of TiO2 nanosheets parallel to the surface of graphene paper. The anisotropic electrode gives a gravimetric capacity of 112 mA h g(-1) at an ultra-high rate of 100 C (corresponding to 36 s of charge-discharge), 3 times higher than that of a referenced isotropic electrode. The results indicate that such an anisotropic electrode can be useful in the search for high-power lithium ion batteries.

  17. 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.

  18. 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.

  19. A lithium electrode with a zinc substrate for secondary batteries

    NASA Astrophysics Data System (ADS)

    Matsuda, Y.; Morita, M.; Katsuma, H.

    1983-03-01

    Koch (1981) and Abraham (1982) have reported work concerning the development of a lithium secondary battery using an organic electrolyte. An efficient Li electrode is a vital factor in connection with the realization of the considered rechargeable batteries. In order to obtain good efficiency in charge-discharge cycling operations, it has been proposed to employ Li negative plates with metal substrates. High coulombic efficiency was achieved using an Al substrate, which forms an alloy with deposited Li during the period of charging. The present investigation is concerned with the charge-discharge characteristics of a Li electrode with a Zn substrate in propylene carbonate solution containing LiClO4 or LiBF4. It is found that the efficiency in the case of a plate with a Zn substrate, which alloys easily with deposited Li, is as high as that obtained in connection with the use of an Al substrate.

  20. The Charge and Discharge Behavior of Molybdenum Trioxide Electrodes in Lithium Perchlorate-Propylene Carbonate Electrolyte.

    DTIC Science & Technology

    1980-07-01

    AMM/§ Diet. specialAK f* I, THE CHARGE AND DISCHARGE BEHAVIOR OF MOLYBDENUM TRIOXIDE ELECTRODES IN LITHIUM PERCHLORATE-PROPYLENE CARBONATE ELECTROLYTE...SHE). Thus, the propylene carbonate oxidation potential is +3.145 V versus SHE or since the potential of the reversible lithium electrode in propylene... carbonate is -3.265 V versus the SHE potential, the solvent oxidation potential should be +6.4 V versus lithium . Thus, another anodic process must be

  1. 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.

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

    PubMed

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

    2016-03-17

    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.

  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

    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.

  5. Recent Progress in Self-Supported Metal Oxide Nanoarray Electrodes for Advanced Lithium-Ion Batteries.

    PubMed

    Zhang, Feng; Qi, Limin

    2016-09-01

    The rational design and fabrication of electrode materials with desirable architectures and optimized properties has been demonstrated to be an effective approach towards high-performance lithium-ion batteries (LIBs). Although nanostructured metal oxide electrodes with high specific capacity have been regarded as the most promising alternatives for replacing commercial electrodes in LIBs, their further developments are still faced with several challenges such as poor cycling stability and unsatisfying rate performance. As a new class of binder-free electrodes for LIBs, self-supported metal oxide nanoarray electrodes have many advantageous features in terms of high specific surface area, fast electron transport, improved charge transfer efficiency, and free space for alleviating volume expansion and preventing severe aggregation, holding great potential to solve the mentioned problems. This review highlights the recent progress in the utilization of self-supported metal oxide nanoarrays grown on 2D planar and 3D porous substrates, such as 1D and 2D nanostructure arrays, hierarchical nanostructure arrays, and heterostructured nanoarrays, as anodes and cathodes for advanced LIBs. Furthermore, the potential applications of these binder-free nanoarray electrodes for practical LIBs in full-cell configuration are outlined. Finally, the future prospects of these self-supported nanoarray electrodes are discussed.

  6. 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.

  7. 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.

  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 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

  10. 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

  11. Measurements of lithium-ion concentration equilibration processes inside graphite electrodes

    NASA Astrophysics Data System (ADS)

    Kindermann, Frank M.; Osswald, Patrick J.; Klink, Stefan; Ehlert, Günter; Schuster, Jörg; Noel, Andreas; Erhard, Simon V.; Schuhmann, Wolfgang; Jossen, Andreas

    2017-02-01

    Methods for estimating inner states in a lithium-ion cell require steady state conditions or accurate models of the dynamic processes. Besides often used inner states such as state-of-charge, state-of-health or state-of-function, relaxation processes strongly influence the mentioned states. Inhomogeneous utilization of electrodes and consequent limitations in the operating conditions have recently been brought to attention. Relaxation measurements after an inhomogeneous current distribution through the thickness of an electrode have not been addressed so far. By using a previously developed laboratory cell, we are able to show an inhomogeneous retrieval of lithium-ions from a graphite electrode through the layer with spatial resolution. After this inhomogeneity caused by a constant current operation, equilibration processes are recorded and can be assigned to two different effects. One effect is an equilibration inside the particles (intra-particle) from surface to bulk and vice versa. The other effect is an assimilation between the particles (inter-particle) to reach a homogeneous state-of-charge in each particle throughout the electrode layer. While intra-particle relaxation is observed to be finished within 4 h, inter-particle relaxation through the layer takes more than 40 h. The overall time for both equilibration processes shows to be in the order of 48 h.

  12. Surface modification agents for lithium batteries

    DOEpatents

    Chen, Zonghai; Amine, Khalil; Belharouak, Ilias

    2015-06-23

    A method includes modifying a surface of an electrode active material including providing a solution or a suspension of a surface modification agent; providing the electrode active material; preparing a slurry of the solution or suspension of the surface modification agent, the electrode active material, a polymeric binder, and a conductive filler; casting the slurry in a metallic current collector; and drying the cast slurry.

  13. 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.

  14. A stable lithium-rich surface structure for lithium-rich layered cathode materials

    NASA Astrophysics Data System (ADS)

    Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

    2016-11-01

    Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g-1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g-1 at 1C (250 mA g-1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface.

  15. A stable lithium-rich surface structure for lithium-rich layered cathode materials

    PubMed Central

    Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

    2016-01-01

    Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

  16. Electrode-Electrolyte Interfaces in Solid Polymer Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Hu, Qichao

    This thesis studies the performance of solid polymer lithium batteries from room temperature to elevated temperatures using mainly electrochemical techniques, with emphasis on the bulk properties of the polymer electrolyte and the electrode-electrolyte interfaces. Its contributions include: 1) Demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence, and improved the conductivity of the graft copolymer electrolyte (GCE) by almost an order of magnitude by changing the ion-conducting block from poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). 2) Identified the rate-limiting step in the battery occurs at the cathode-electrolyte interface using both full cell and symmetric cell electrochemical impedance spectroscopy (EIS), improved the battery rate capability by using the GCE as both the electrolyte and the cathode binder to reduce the resistance at the cathode-electrolyte interface, and used TEM and SEM to visualize the polymer-particle interface (full cells with LiFePO4 as the cathode active material and lithium metal as the anode were assembled and tested). 3) Applied the solid polymer battery to oil and gas drilling application, performed high temperature (up to 210 °C) cycling (both isothermal and thermal cycling), and demonstrated for the first time, current exchange between a solid polymer electrolyte and a liquid lithium metal. Both the cell open-circuit-voltage (OCV) and the overall GCE mass remained stable up to 200 °C, suggesting that the GCE is electrochemically and gravimetrically stable at high temperatures. Used full cell EIS to study the behavior of the various battery parameters as a function of cycling and temperature. 4) Identified the thermal instability of the cell was due to the reactivity of lithium metal and its passivation film at high temperatures, and used Li/GCE/Li symmetric cell

  17. Electrode architectures for enhanced lithium ion battery performance

    NASA Astrophysics Data System (ADS)

    Kotz, Sharon Loeffler

    Increasing prevalence of portable electronic devices and growing concern over the consumption of fossil fuels have led to a growing demand for more efficient energy storage options. Lithium ion chemistry has grown to dominate the battery market, but still requires improvement to meet the increasing need for smaller, cheaper, better performing batteries. The use of nanomaterials has garnered much attention in recent years as a potential way of improving battery performance while decreasing the size. However, new problems are introduced with these materials such as low packing density and high reactivity with the electrolyte. This research focuses on the development of an electrode architecture using nanomaterials which will decrease lithium ion transport distance while enhancing electrical conductivity within the cell. The proposed architecture consists of a stacked, 2D structure composed of layers of carbon nanotubes and active material particles, and can be applied to both the anode and the cathode. The process also has the advantage of low cost because it can be performed under normal laboratory conditions (e.g. temperature and pressure) and easily adapted to a commercial scale.

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

    DOE PAGES

    Li, Jianlin; Daniel, Claus; Wood, III, David L.; ...

    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.

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

    SciTech Connect

    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.

  20. Synthesis, characterization, and electrochemical investigation of novel electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Kerr, Tracy Alexandra

    2002-08-01

    As the demand for better energy storage devices increases, finding new materials capable of improvement on existing technology becomes essential. Within this body of work, several new electrode materials of different structure type have been synthesized, characterized, and evaluated for their lithium insertion/deinsertion behavior in lithium ion batteries. Nanocomposites of novel alloy, and convertible oxide anode materials have been studied. Nanoparticles of Ge and Sn that are able to form lithium rich alloys have been synthesized, and their low potential lithium insertion behavior studied. In order to inhibit agglomeration of the tiny particles, a novel synthesis route was designed to attach ionically conducting polymers to their surfaces. Characterization by a combination of techniques (XRD, TEM, SEM and FTIR spectroscopy) verified the existence of nanoparticles embedded in a polymer matrix, albeit with some impurities. Electrochemical data show that even when the lithium insertion capacity within these materials is high, the process is extremely irreversible as lithium ions become trapped within the matrix, and only a very small anodic capacity is realized. The first convertible polymer/oxide nanocomposite (poly(para-phenylene)/MoO 3) to be evaluated as an anode material was synthesized using a novel surfactant mediated method. XRD data indicated a 5.2 A increase in the MoO3 layer spacing to 12.1 A after polymer incorporation. Low potential electrochemical insertion properties show that the polymer/oxide nanocomposite behaves in a similar manner to the host MoO3 material. A variety of cathode materials were also synthesized and evaluated for their high potential lithium insertion properties. A comparative study on the effect that synthetic procedure may have on the electrochemical properties of the poly(aniline)/MoO3 cathode material have been studied. Poly(aniline)/MoO 3 nanocomposites have been synthesized from a solution insertion route and via hydrothermal

  1. 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.

  2. 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

  3. 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.

  4. A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries.

    PubMed

    Fang, Xin; Peng, Huisheng

    2015-04-01

    As a promising candidate for future batteries, the lithium-sulfur battery is gaining increasing interest due to its high capacity and energy density. However, over the years, lithium-sulfur batteries have been plagued by fading capacities and the low Coulombic efficiency derived from its unique electrochemical behavior, which involves solid-liquid transition reactions. Moreover, lithium-sulfur batteries employ metallic lithium as the anode, which engenders safety vulnerability of the battery. The electrodes play a pivotal role in the performance of lithium-sulfur batteries. A leap forward in progress of lithium-sulfur batteries is always accompanied by a revolution in the electrode technology. In this review, recent progress in rechargeable lithium-sulfur batteries is summarized in accordance with the evolution of the electrodes, including the diversified cathode design and burgeoning metallic-lithium-free anodes. Although the way toward application has still many challenges associated, recent progress in lithium-sulfur battery technology still paints an encouraging picture of a revolution in rechargeable batteries.

  5. 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.

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

    DOE PAGES

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; ...

    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

  7. 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.

  8. 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).

  9. Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

    NASA Astrophysics Data System (ADS)

    Lim, Cheolwoong; Yan, Bo; Kang, Huixiao; Song, Zhibin; Lee, Wen Chao; De Andrade, Vincent; De Carlo, Francesco; Yin, Leilei; Kim, Youngsik; Zhu, Likun

    2016-10-01

    To investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO2) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO2, polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm3 packing density and 4 C rate.

  10. 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.

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

    DOEpatents

    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.

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

    NASA Astrophysics Data System (ADS)

    Sun, Xiao-Guang; Dai, Sheng

    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 LiPF 6/EC-PC-DMC (1/1/3, w/w/w) and 1.0 M LiBF 4/EC-PC-DMC (1/1/3, w/w/w) under a current density of 0.075 mA cm -2. LM was also used as an additive to the electrolyte of 1.0 M LiPF 6/EC-DMC-DEC (1/1/1, v/v/v) 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 LiCoO 2 electrodes.

  13. 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.

  14. Mechanical measurements on lithium phosphorous oxynitride coated silicon thin film electrodes for lithium-ion batteries during lithiation and delithiation

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The development of large stresses during lithiation and delithiation drives mechanical and chemical degradation processes (cracking and electrolyte decomposition) in thin film silicon anodes that complicate the study of normal electrochemical and mechanical processes. To reduce these effects, lithium phosphorous oxynitride (LiPON) coatings were applied to silicon thin film electrodes. Applying a LiPON coating has two purposes. First, the coating acts as a stable artificial solid electrolyte interphase. Second, it limits mechanical degradation by retaining the electrode's planar morphology during cycling. The development of stress in LiPON-coated electrodes was monitored using substrate curvature measurements. LiPON-coated electrodes displayed highly reproducible cycle-to-cycle behavior, unlike uncoated electrodes which had poorer coulombic efficiency and exhibited a continual loss in stress magnitude with continued cycling due to film fracture. The improved mechanical stability of the coated silicon electrodes allowed for a better investigation of rate effects and variations of mechanical properties during electrochemical cycling.

  15. 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.

  16. 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

  17. Effects of the electrolyte composition on the electrode characteristics of rechargeable lithium batteries

    SciTech Connect

    Morita, Masayuki; Ishikawa, Masashi; Matsuda, Yoshiharu

    1995-12-31

    A variety of organic solvent-based electrolytes have been studied for ambient temperature, rechargeable lithium (ion) batteries. The ionic behavior of the electrolyte system was investigated through conductivity measurements. The electrochemical characteristics of carbon-based materials (carbon fiber and graphite) as the negative electrode were examined in different compositions of the organic electrolytes. The electrolyte composition as well as the structure of the electrode material greatly influenced the charge/discharge profiles of the electrode.

  18. 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

  19. 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.

  20. A structural study of solid electrolyte interface on negative electrode of lithium-Ion battery by electron microscopy.

    PubMed

    Matsushita, Tadashi; Watanabe, Jiro; Nakao, Tatsuya; Yamashita, Seiichi

    2014-11-01

    For the last decades, the performance of the lithium-ion battery (LIB) has been significantly improved and its applications have been expanding rapidly. However, its performance has yet to be enhanced.In the lithium-ion battery development, it is important to elucidate the electrode structure change in detail during the charge and discharge cycling. In particular, solid electrolyte interface (SEI) formed by decomposition of the electrolytes on the graphite negative electrode surface should play an important role for battery properties. Therefore, it is essential to control the structure and composition of SEI to improve the battery performance. Here, we conducted a scanning electron microscope (SEM) and transmission electron microscope (TEM) study to elucidate the structures of the SEI during the charge and discharge process using LiNi1/3Co1/3Mn1/3O2 [1] cathode and graphite anode. [2] Since SEI is a lithium-containing compound with high activity, it was observed without being exposed to the atmosphere. The electrodes including SEI were sampled after dismantling batteries with cutoff voltages of 3V and 4.2V for the charge process and 3V for the discharge process. Fig.1 shows SEM images of the graphite electrode surface during the charge and discharge process. The change of the SEI structure during the process was clearly observed. Further, TEM images showed that the SEI grew thicker during the charge process and becomes thinner when discharged. These results with regard to the reversible SEI structure could give a new insight for the battery development.jmicro;63/suppl_1/i21/DFU056F1F1DFU056F1Fig. 1.SEM images of the graphite electrode surface:(a) before charge process;(b) with charge-cutoff voltage of 3.0V; (c) with charge-cutoff voltage of 4.2V; (d) with discharge-cutoff voltage of 3.0V.

  1. 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.

  2. 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.

  3. Lithium-assisted plastic deformation of silicon electrodes in lithium-ion batteries: a first-principles theoretical study.

    PubMed

    Zhao, Kejie; Wang, Wei L; Gregoire, John; Pharr, Matt; Suo, Zhigang; Vlassak, Joost J; Kaxiras, Efthimios

    2011-07-13

    Silicon can host a large amount of lithium, making it a promising electrode for high-capacity lithium-ion batteries. Recent experiments indicate that silicon experiences large plastic deformation upon Li absorption, which can significantly decrease the stresses induced by lithiation and thus mitigate fracture failure of electrodes. These issues become especially relevant in nanostructured electrodes with confined geometries. On the basis of first-principles calculations, we present a study of the microscopic deformation mechanism of lithiated silicon at relatively low Li concentration, which captures the onset of plasticity induced by lithiation. We find that lithium insertion leads to breaking of Si-Si bonds and formation of weaker bonds between neighboring Si and Li atoms, which results in a decrease in Young's modulus, a reduction in strength, and a brittle-to-ductile transition with increasing Li concentration. The microscopic mechanism of large plastic deformation is attributed to continuous lithium-assisted breaking and re-forming of Si-Si bonds and the creation of nanopores.

  4. High voltage, rechargeable lithium batteries using newly-developed carbon for negative electrode material

    NASA Astrophysics Data System (ADS)

    Yamaura, Junichi; Ozaki, Yoshiyuki; Morita, Akiyoshi; Ohta, Akira

    1993-03-01

    Carbon is a good candidate for negative electrodes because it can take the form of lithium intercalation compounds. We discussed the characteristics of typical carbon materials which have been studied as negative electrode materials. We have found that the mesophase pitch-based carbon microbead (MCMB) of high graphitization stage which have been graphitized at a high temperature such as 2800 C gives good characteristics as a negative electrode for rechargeable lithium batteries. The cylindrical 'AA-size' batteries of our trial products using LiCoO2 as the positive electrode and the M CMB graphitized at 2800 C as the negative electrode have been found to provide large capacities of 500 mA h and high voltages of 3.7 V with high energy densities of 240 W h/l, 100 W h/kg.

  5. 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

  6. 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

    2015-01-28

    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.

  7. 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.

  8. 3D mapping of lithium in battery electrodes using neutron activation

    NASA Astrophysics Data System (ADS)

    He, Yuping; Downing, R. Gregory; Wang, Howard

    2015-08-01

    The neutron depth profiling technique based on the neutron activation reaction, 6Li (n, α) 3H, was applied with two dimensional (2D) pinhole aperture scans to spatially map lithium in 3D. The technique was used to study model LiFePO4 electrodes of rechargeable batteries for spatial heterogeneities of lithium in two cathode films that had undergone different electrochemical cycling histories. The method is useful for better understanding the functioning and failure of batteries using lithium as the active element.

  9. 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.

  10. 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

    2016-04-05

    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. 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.

  11. 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.

  12. 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.

  13. Electrochemical reduction of an anion for ionic-liquid molecules on a lithium electrode studied by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ando, Yasunobu; Kawamura, Yoshiumi; Ikeshoji, Tamio; Otani, Minoru

    2014-09-01

    We report ab initio molecular dynamics studies with electric field that reveal chemical stability of room temperature ionic liquid for charge transfer from lithium and nickel electrodes. Bis(trifluoromethanesulfonyl)imide (TFSI) is oxidized on the nickel electrode under a high positive bias condition as expected. However, TFSI is reduced on the lithium electrode under both positive and negative bias conditions, because the lithium electrode acts as a strong reductant. The decomposition of TFSI anion might induce the formation of LiF as a solid electrolyte interphase, which could restrain the TFSI reduction. The stability of an cation under reductant conditions is presented.

  14. 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.

  15. 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.

  16. Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries.

    PubMed

    Kalluri, Sujith; Yoon, Moonsu; Jo, Minki; Liu, Hua Kun; Dou, Shi Xue; Cho, Jaephil; Guo, Zaiping

    2017-03-02

    Cathode material degradation during cycling is one of the key obstacles to upgrading lithium-ion and beyond-lithium-ion batteries for high-energy and varied-temperature applications. Herein, we highlight recent progress in material surface-coating as the foremost solution to resist the surface phase-transitions and cracking in cathode particles in mono-valent (Li, Na, K) and multi-valent (Mg, Ca, Al) ion batteries under high-voltage and varied-temperature conditions. Importantly, we shed light on the future of materials surface-coating technology with possible research directions. In this regard, we provide our viewpoint on a novel hybrid surface-coating strategy, which has been successfully evaluated in LiCoO2 -based-Li-ion cells under adverse conditions with industrial specifications for customer-demanding applications. The proposed coating strategy includes a first surface-coating of the as-prepared cathode powders (by sol-gel) and then an ultra-thin ceramic-oxide coating on their electrodes (by atomic-layer deposition). What makes it appealing for industry applications is that such a coating strategy can effectively maintain the integrity of materials under electro-mechanical stress, at the cathode particle and electrode- levels. Furthermore, it leads to improved energy-density and voltage retention at 4.55 V and 45 °C with highly loaded electrodes (≈24 mg.cm(-2) ). Finally, the development of this coating technology for beyond-lithium-ion batteries could be a major research challenge, but one that is viable.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Reversible and irreversible dilation of lithium-ion battery electrodes investigated by in-situ dilatometry

    NASA Astrophysics Data System (ADS)

    Sauerteig, Daniel; Ivanov, Svetlozar; Reinshagen, Holger; Bund, Andreas

    2017-02-01

    The technique of electrochemical in-situ dilatometry is applied to study the intercalation induced macroscopic expansion of electrodes for lithium-ion batteries. A full cell setup is used to investigate the expansion under real conditions. This method enables in-situ measurement of expansion under defined pressure, using conventional electrodes, separators and electrolytes. To understand the influence of the microstructure, the swelling behavior of different LiNi1/3 Mn1/3 Co1/3 O2 (NMC) positive electrodes and graphite negative electrodes is measured and systematically analyzed. A theoretical approach for assessment of reversible electrode displacement in a full cell is developed, by using a low number of material specific input parameters. Electrochemical in-situ dilatometry is able to show differences in irreversible dilation depending on electrode design and therefore it is a powerful technique for stability and lifetime assessment.

  2. Plasma processes in the preparation of lithium-ion battery electrodes and separators

    NASA Astrophysics Data System (ADS)

    Nava-Avendaño, J.; Veilleux, J.

    2017-04-01

    Lithium-ion batteries (LIBs) are the energy storage devices that dominate the portable electronic market. They are now also considered and used for electric vehicles and are foreseen to enable the smart grid. Preparing batteries with high energy and power densities, elevated cycleability and improved safety could be achieved by controlling the microstructure of the electrode materials and the interaction they have with the electrolyte over the working potential window. Selecting appropriate precursors, reducing the preparation steps and selecting more efficient synthesis methods could also significantly reduce the costs of LIB components. Implementing plasma technologies can represent a high capital investment, but the versatility of the technologies allows the preparation of powdered nanoparticles with different morphologies, as well as with carbon and metal oxide coatings. Plasma technologies can also enable the preparation of binder-free thin films and coatings for LIB electrodes, and the treatment of polymeric membranes to be used as separators. This review paper aims at highlighting the different thermal and non-thermal plasma technologies recently used to synthesize coated and non-coated active materials for LIB cathodes and anodes, and to modify the surface of separators.

  3. FeS@C on Carbon Cloth as Flexible Electrode for Both Lithium and Sodium Storage.

    PubMed

    Wei, Xiang; Li, Weihan; Shi, Jin-an; Gu, Lin; Yu, Yan

    2015-12-23

    Flexible and self-supported carbon-coated FeS on carbon cloth films (denoted as FeS@C/carbon cloth) is prepared by a facial hydrothermal method combined with a carbonization treatment. The FeS@C/carbon cloth could be directly used as electrodes for Li-ion batteries (LIBs) and sodium-ion batteries (NIBs). The synthetic effects of the structure, highly electron-conductive of carbon cloth, porous structure for electrolyte access, and uniform carbon shell on FeS surface to accommodate the volume change lead to improved cyclability and rate capability. For lithium storage, the FeS@C/carbon cloth electrode delivers a high discharge capacity of 420 mAh g(-1) even after 100 cycles at a current density of 0.15 C and 370 mAh g(-1)at a high current density of 7.5 C (1 C = 609 mA g(-1). When used for sodium storage, it keeps a reversible capacity of 365 mAh g(-1)after 100 cycles at 0.15 C. Similar process can be utilized for the formation of various cathode and anode composites on carbon cloth for flexible energy storage devices.

  4. 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

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

    DOEpatents

    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.

  6. Lithium Storage Mechanisms in Purpurin Based Organic Lithium Ion Battery Electrodes

    DTIC Science & Technology

    2012-12-11

    Advances in Lithium-ion batteries (Kluwer Academic/Plenum, New York, 2002). 7. Mizushima, K., Jones, P. C., Wiseman, P. J. & Goodenough , J. B. LixCoO2 (0...P. G. & Goodenough , J. B. Electrochemical extraction of lithium from LiMn2O4. Mat. Res. Bull. 18, 461 (1983). 9. Recham, N., Chotard, J. N., Dupont

  7. Structural optimization of 3D porous electrodes for high-rate performance lithium ion batteries.

    PubMed

    Ye, Jianchao; Baumgaertel, Andreas C; Wang, Y Morris; Biener, Juergen; Biener, Monika M

    2015-02-24

    Much progress has recently been made in the development of active materials, electrode morphologies and electrolytes for lithium ion batteries. Well-defined studies on size effects of the three-dimensional (3D) electrode architecture, however, remain to be rare due to the lack of suitable material platforms where the critical length scales (such as pore size and thickness of the active material) can be freely and deterministically adjusted over a wide range without affecting the overall 3D morphology of the electrode. Here, we report on a systematic study on length scale effects on the electrochemical performance of model 3D np-Au/TiO2 core/shell electrodes. Bulk nanoporous gold provides deterministic control over the pore size and is used as a monolithic metallic scaffold and current collector. Extremely uniform and conformal TiO2 films of controlled thickness were deposited on the current collector by employing atomic layer deposition (ALD). Our experiments demonstrate profound performance improvements by matching the Li(+) diffusivity in the electrolyte and the solid state through adjusting pore size and thickness of the active coating which, for 200 μm thick porous electrodes, requires the presence of 100 nm pores. Decreasing the thickness of the TiO2 coating generally improves the power performance of the electrode by reducing the Li(+) diffusion pathway, enhancing the Li(+) solid solubility, and minimizing the voltage drop across the electrode/electrolyte interface. With the use of the optimized electrode morphology, supercapacitor-like power performance with lithium-ion-battery energy densities was realized. Our results provide the much-needed fundamental insight for the rational design of the 3D architecture of lithium ion battery electrodes with improved power performance.

  8. In situ-formed Li2S in lithiated graphite electrodes for lithium-sulfur batteries.

    PubMed

    Fu, Yongzhu; Zu, Chenxi; Manthiram, Arumugam

    2013-12-04

    Rechargeable lithium-sulfur (Li-S) batteries have the potential to meet the high-energy demands of the next generation of batteries. However, the lack of lithium in the sulfur cathode requires the use of lithium metal anode, posing safety hazards. Use of Li2S as the cathode can eliminate this problem, but it is hampered by intrinsic challenges (e.g., high electrical resistivity and reactivity in air). We report here the use of a lithiated graphite electrode to chemically reduce in situ the polysulfide Li2S6 in liquid electrolyte to insoluble Li2S. The chemical reduction slowly draws lithium out of graphite, resulting in a reduction of the d002 spacing of graphite from 3.56 to 3.37 Å and an increase in the open-circuit voltage of cells from 60 mV to 2.10 V after stabilizing over 6 days. X-ray photoelectron spectroscopic analysis shows 48.4% of sulfur in the polysulfide was converted to Li2S. The formed amorphous Li2S shows good cyclability with low charge overpotential. The results demonstrate that lithiated graphite can serve as a lithium donor in lithium-deficient cathodes, which could enable lithium metal-free Li-S, Li-air, or Li-organic batteries.

  9. 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

  10. 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

    2016-02-01

    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.

  11. 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.

  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. 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.

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

    DOE PAGES

    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

  15. 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.

  16. All-solid-state lithium-sulfur batteries with three-dimensional mesoporous electrode structures

    NASA Astrophysics Data System (ADS)

    Nagao, Miki; Suzuki, Kota; Imade, Yuki; Tateishi, Mitsuru; Watanabe, Ryota; Yokoi, Toshiyuki; Hirayama, Masaaki; Tatsumi, Takashi; Kanno, Ryoji

    2016-10-01

    Although the characteristics of lithium-sulfur batteries are advantageous for various applications, batteries with liquid electrolytes show capacity fading due to the dissolution of polysulfides. All-solid-state lithium-sulfur batteries with highly reversible characteristics are developed using a three-dimensional carbon matrix framework structure for the sulfur cathode. Sulfur is introduced into a carbon replica framework with a pore size of 8-100 nm. The composite electrode structure provides high electronic conduction and allows high cathode utilization during the battery reaction. The capacity of cells using a LiAl alloy as the negative electrode and the thio-LISICON (lithium superionic conductor) electrolyte increases when the pore size of the carbon replica is decreased from 100 nm to less than 15 nm. The highest capacity is obtained for the carbon replica with a pore size of 8.6 nm and a wall thickness of 4.7 nm. An examination of the relationship between the charge-discharge capacity and the structure of carbon replicas with different pore sizes and wall thicknesses indicates that three-dimensional highly ordered mesoporous carbon with a small pore size is a promising electrode structure for lithium-sulfur all-solid-state batteries.

  17. Lithium Surface Coatings and Improved Plasma Performance in NSTX

    NASA Astrophysics Data System (ADS)

    Kugel, H. W.

    2007-11-01

    NSTX research on lithium-coated plasma facing components is the latest step in a decade-long, multi-institutional research program to develop lithium as a plasma-facing system that can withstand the high heat and neutron fluxes in a DT reactor. The NSTX research is also aimed towards sustaining the current non- inductively in H-mode plasmas which requires control of both wall recycling and impurity influxes. Employing several techniques to coat the plasma facing components (PFCs) with lithium, NSTX experiments have shown, for the first time, significant benefits in high-power divertor plasmas. Lithium pellet injection (LPI) uses the plasma itself to distribute lithium on the divertor or limiter surfaces. The multi-barrel LPI on NSTX can introduce either lithium pellets with masses 1 - 5 mg or powder during a discharge. This significantly lowered recycling and reduced the density in a subsequent NBI-heated, divertor plasma. Lithium coatings have also been applied with a LIThium EvaporatoR (LITER) that was installed on an upper vacuum vessel port to direct a collimated stream of lithium vapor toward the graphite tiles of the lower center stack and divertor. The lithium was evaporated either before tokamak discharges, or continuously between and during them. By evaporating lithium into the helium glow discharge that typically precedes each tokamak discharge, a coating of the entire PFC area was achieved. Lithium depositions from a few mg to 1 g have been applied between discharges. Among the effects observed in subsequent neutral-beam heated plasmas were decreases in oxygen impurities, plasma density, and the inductive flux consumption, and increases in electron temperature, ion temperature, energy confinement and DD neutron rate. In addition, a reduction in the ELM frequency, including their complete suppression, was achieved in H-mode plasmas. Additional observations, such as, the duration of the lithium coatings, increases in core metal impurity radiation, and

  18. Conductive Polymer Binder for High-Tap-Density Nanosilicon Material for Lithium-Ion Battery Negative Electrode Application.

    PubMed

    Zhao, Hui; Wei, Yang; Qiao, Ruimin; Zhu, Chenhui; Zheng, Ziyan; Ling, Min; Jia, Zhe; Bai, Ying; Fu, Yanbao; Lei, Jinglei; Song, Xiangyun; Battaglia, Vincent S; Yang, Wanli; Messersmith, Phillip B; Liu, Gao

    2015-12-09

    High-tap-density silicon nanomaterials are highly desirable as anodes for lithium ion batteries, due to their small surface area and minimum first-cycle loss. However, this material poses formidable challenges to polymeric binder design. Binders adhere on to the small surface area to sustain the drastic volume changes during cycling; also the low porosities and small pore size resulting from this material are detrimental to lithium ion transport. This study introduces a new binder, poly(1-pyrenemethyl methacrylate-co-methacrylic acid) (PPyMAA), for a high-tap-density nanosilicon electrode cycled in a stable manner with a first cycle efficiency of 82%-a value that is further improved to 87% when combined with graphite material. Incorporating the MAA acid functionalities does not change the lowest unoccupied molecular orbital (LUMO) features or lower the adhesion performance of the PPy homopolymer. Our single-molecule force microscopy measurement of PPyMAA reveals similar adhesion strength between polymer binder and anode surface when compared with conventional polymer such as homopolyacrylic acid (PAA), while being electronically conductive. The combined conductivity and adhesion afforded by the MAA and pyrene copolymer results in good cycling performance for the high-tap-density Si electrode.

  19. 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.

  20. Simulation of capacity loss in carbon electrode for lithium-ion cells during storage

    NASA Astrophysics Data System (ADS)

    Ramasamy, Ramaraja P.; Lee, Jong-Won; Popov, Branko N.

    A mathematical model was developed which simulates the self-discharge capacity losses in the carbon anode for a SONY 18650 lithium-ion battery. The model determines the capacity loss during storage on the basis of a continuous reduction of organic solvent and de-intercalation of lithium at the carbon/electrolyte interface. The state of charge, open circuit potential, capacity loss and film resistance on the carbon electrode were calculated as a function of storage time using different values of rate constant governing the solvent reduction reaction.

  1. 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.

  2. 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

  3. Advanced Materials for Neural Surface Electrodes.

    PubMed

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

    2014-12-01

    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.

  4. 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

  5. The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

    DOE PAGES

    Somerville, L.; Bareno, J.; Trask, S.; ...

    2016-10-22

    Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

  6. The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

    SciTech Connect

    Somerville, L.; Bareno, J.; Trask, S.; Jennings, P.; McGordon, A.; Lyness, C.; Bloom, Ira

    2016-10-22

    Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, we found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.

  7. The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

    NASA Astrophysics Data System (ADS)

    Somerville, L.; Bareño, J.; Trask, S.; Jennings, P.; McGordon, A.; Lyness, C.; Bloom, I.

    2016-12-01

    Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650-type cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, we found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode "jelly roll". This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. This non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.

  8. 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.

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

    DOE PAGES

    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

  10. TiO2(B) nanoribbons as negative electrode material for lithium ion batteries with high rate performance.

    PubMed

    Beuvier, Thomas; Richard-Plouet, Mireille; Mancini-Le Granvalet, Maryline; Brousse, Thierry; Crosnier, Olivier; Brohan, Luc

    2010-09-20

    Nanosized TiO(2)(B) has been investigated as a possible candidate to replace Li(4)Ti(5)O(12) or graphite as the negative electrode for a Li-ion battery. Nanoribbon precursors, classically synthesized in autogenous conditions at temperatures higher than 170 °C in alkaline medium, have been obtained, under reflux (T ∼ 120 °C, P = 1 bar). After ionic exchange, these nanoribbons exhibit a surface area of 140 m(2) g(-1), larger than those obtained under autogenous conditions or by solid state chemistry. These nanoparticles transform after annealing to isomorphic titanium dioxide. They mainly crystallize as the TiO(2)(B) variety with only 5% of anatase. This quantification of the anatase/TiO(2)(B) ratio was deduced from Raman spectroscopy measurement. TEM analysis highlights the excellent crystallinity of the nanosized TiO(2)(B), crystallizing as 6 nm thin nanoribbons. These characteristics are essential in lithium batteries for a fast lithium ion solid state diffusion into the active material. In lithium batteries, the TiO(2)(B) nanoribbons exhibit a good capacity and an excellent rate capability (reversible capacity of 200 mA h g(-1) at C/3 rate (111 mA g(-1)), 100 mA h g(-1) at 15C rate (5030 mA g(-1)) for a 50% carbon black loaded electrode). The electrode formulation study highlights the importance of the electronic and ionic connection around the active particles. The cycleability of the nano-TiO(2)(B) is another interesting point with a capacity loss of 5% only, over 500 cycles at 3C.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Electrochemical and thermodynamic studies of the electrode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Bang, Hyun Joo

    A series of graphite samples were tested for their electrochemical performance as anode material for lithium ion cells. Specially treated natural graphite samples showed good reversible capacities and relatively small irreversible capacity losses. The good performance of these samples can be explained by the low surface area associated with the rounded edges and absence of exfoliation due to the presence of the rhombohedral phase and defects in the grain boundaries. Graphitized cokes showed larger irreversible capacity losses while mesophase carbons showed lower reversible capacity. The treated natural graphite samples, especially LBG25 were found to be high performance, low cost anode materials for the lithium ion cells. The electrochemical and thermal behaviors of the spinels---LiMn 2O4, LiCo1/6Mn11/6O4, LiFe 1/6Mn11/6O4, and LiNi1/6Mn11/6 O4 were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge/discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention(GITT) was observed for the substituted spinels (0.11% loss/cycle for LiCo1/6Mn 11/6O4; 0.3% loss/cycle for LiFe1/6Mn11/6 O4; and 0.2% loss/cycle for LiNi1/6Mn11/6 O4) than for the lithium manganese dioxide spinel (1.6% loss/cycle for first 10 cycles, 0.9% loss/cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry (DSC) results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels. The thermal profile of LiMn2O4 and LiAl0.17 Mn1.83O3.97S0.03 was measured in an isothermal micro-calorimeter. The heat contributions are discussed in terms of reversible and irreversible heat generation, in combination with the entropy change directly obtained by the dE/dT measurements and the over-potential measurements. The endothermic and exothermic heat

  19. Performance degradation of high-power lithium-ion cells-Electrochemistry of harvested electrodes

    NASA Astrophysics Data System (ADS)

    Abraham, D. P.; Knuth, J. L.; Dees, D. W.; Bloom, I.; Christophersen, J. P.

    The performance of 18650-type high-power lithium-ion cells is being evaluated as part of the U.S. Department of Energy's (DOEs) Advanced Technology Development (ATD) program. In this article, we present accelerated aging data acquired on 18650-cells containing LiNi 0.8Co 0.15Al 0.05O 2- or LiNi 0.8Co 0.1Al 0.1O 2-based positive electrodes, MAG-10 graphite-based negative electrodes, and 1.2-M LiPF 6 in EC:EMC (3:7 by wt.) electrolyte. Capacity and impedance data acquired on electrodes harvested from these cells highlight the contributions of the positive and negative electrodes to the degradation of cell performance. We also describe test methodologies used to examine the electrochemical characteristics of the harvested electrodes. Identifying and optimizing cell components responsible for performance degradation should enable the development of new lithium-ion cell chemistries that will meet the 15-year cell calendar life goal established by DOEs FreedomCar initiative.

  20. 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.

  1. 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

  2. Mapping redox energies of electrode materials for lithium batteries

    NASA Astrophysics Data System (ADS)

    Padhi, Akshaya Kumar

    A comparative study of oxides containing tetrahedral polyanions forming 3D-framework host structures with octahedral-site transition-metal oxidant cations addresses the following issues: (i) Chemical versatility of the framework structures allows one to determine the redox couples for different transition-metal cations with respect to the Fermi energy of a lithium anode and how they vary with changes of host structure, choice of polyanion, or degree of lithiation. (ii) Exploration of the advantage of a more open framework for Li+-ion diffusion versus the disadvantage of polaronic conduction. (iii) Identification of the cause of a reversible capacity fade with increasing current density. (iv) The design of new materials for secondary batteries. Variation of a redox energy at an M atom in an oxide depends on two factors: (a) the Madelung energy of the cation and (b) the covalent contribution to the M-O bonding, which may be modulated by a counter cation through the inductive effect. Electrochemical characterization of the spinel system Li1+x[ Mn1.5M0.5] O4, M = Co or Ni, indicates an overlap of the Mn4+/Mn3+ and M3+/M2+ redox energies at x = 0.5. The family of V (LiM) O4 spinels with M = Mn, Co or Ni has M3+/M2+ redox couples at 3.8, 4.2, and 4.8 eV, respectively, below the Fermi energy of a lithium anode, which indicates formation of (VO4)3- polyanions. Replacement of VO4 by PO4 yields ordered- olivine structures LiMPO4; Li1-xFePO4 and Li1-xFe0.5Mn0.5PO4 show Fe3+/Fe2+ and Mn3+/Mn2+ redox couples at 3.4 and 4.1 V vs. lithium, respectively. Reversible Li insertion into FePO4 retains a 3.4 V plateau vs. lithium with increasing current density, but shows a capacity that fades reversibly with current density as a result of a dynamic process. A change of about 0.8 eV between isostructural sulfates and phosphates for the Ti4/Ti3+, V3+/V2+ and Fe3+/Fe2+ couples is due to the inductive effect. These shifts illustrate that the relative positions of the redox energies remain

  3. 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

    2016-04-06

    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.

  4. Nanocomposite Electrodes for Advanced Lithium Batteries: The LiFePO4 Cathode

    DTIC Science & Technology

    2001-11-01

    The LiFePO4 Cathode DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: Nanophase and...Nanocomposite Electrodes for Advanced Lithium Batteries: The LiFePO4 Cathode Shoufeng Yang, Yanning Song, Peter Y. Zavalij and M. Stanley Whittingham...Institute for Materials Research, Binghamton University, Binghamton, NY 13902-1600, U.S.A. ABSTRACT LiFePO4 was successfully synthesized by high temperature

  5. Solid-State Electrode Engineering and Material Processing for All-Solid-State Lithium and Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Yersak, Thomas A.

    In this dissertation we demonstrate the full rechargeability of a FeS 2/lithium metal battery at 60°C. To enable the reversibility of the FeS2 redox chemistry we utilize a bulk all-solid-state battery architecture based upon the Li2S-P2S5 glass-ceramic electrolyte. The glass-ceramic electrolyte's non-volatility and non-flammability allows us to use a lithium metal anode safely, while its solid nature confines FeS2's intermediate electroactive species to prevent active material loss and capacity fade. Based only on the weight of the active materials our battery stands to triple the specific energy (Wh kg-1) of conventional state-of-the-art Li-ion batteries. We also observe ortho-FeS2 as a charge product and propose a new discharge mechanism which revises 30 years of research on the subject. Unfortunately, our laboratory FeS2/Li battery could not achieve a practical cell-level specific energy because the composite electrode was nearly 70 wt. % glass-ceramic electrolyte and carbon black. We also found that our batteries were not durable because the formation of lithium dendrites through the glass-ceramic electrolyte separator membrane frequently internally shorted test cells upon charge. The remainder of this dissertation outlines our work to develop an all-solid-state Li-ion battery to address the shorting issue and the work done to engineer better active material-electrolyte solid-solid interfaces in the composite electrode for high cell-level specific energy.

  6. Improved electrochemical performance of SnO2-mesoporous carbon hybrid as a negative electrode for lithium ion battery applications.

    PubMed

    Srinivasan, N R; Mitra, Sagar; Bandyopadhyaya, Rajdip

    2014-04-14

    To utilize the high specific capacity of SnO2 as an anode material in lithium-ion batteries, one has to overcome its poor cycling performance and rate capability, which result from large volume expansion (∼300%) of SnO2 during charging-discharging cycles. Hence, to accommodate the volume change during cycling, SnO2 nanoparticles of 6 nm diameter were synthesized specifically only on the outer surface of the mesopores, present within mesoporous carbon (CMK-5) particles, resulting in an effective buffering layer. To that end, the synthesis process first involves the formation of 3.5 nm SnO2 nanoparticles inside the mesopores of mesoporous silica (SBA-15), the latter being used as a template subsequently to obtain SnO2-CMK-5 hybrid particles. SnO2-CMK-5 exhibits superior rate capabilities, e.g. after 30 cycles, a specific discharge capacity of 598 mA h g(-1), at a current density of 178 mA g(-1). Electrochemical impedance spectroscopy reveals that the SnO2-CMK-5 electrode undergoes a significant reduction in solid-electrolyte interfacial and charge transfer resistances, with a simultaneous increase in the diffusion coefficient of lithium ions, all these in comparison to an electrode made of only SnO2 nanoparticles. This enhances the potential of using the SnO2-CMK-5 hybrid as a negative electrode, in terms of improved discharge capacity and cycling stability, compared to other electrodes, such as only SnO2 or only CMK-5.

  7. Vertically Aligned Carbon Nanotube Electrodes for Lithium-Ion Batteries

    DTIC Science & Technology

    2011-01-01

    includes, but is not limited to, cobalt oxide [8] and phospho-olivine [9] nanoparticles, cobalt oxide [10] and silicon ∗ Corresponding author. Tel.: +1 937...wpafb.af.mil (M.F. Durstock). [11] nanowires , and iron oxide/copper [12] and tin/copper [13] nanorods. Carbon nanotubes (CNTs) have also been examined as...MWNTs (without any polymeric binders or conduc- tive carbon additives) as the electrodes. A porous polypropylene film infiltrated with a solution of

  8. Kinetic characteristics of mixed conductive electrodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Ma, Jianxin; Wang, Chunsheng; Wroblewski, Shannon

    The rate performances of four mixed conductive electrodes (Li 4/3Ti 5/3O 4, LiFePO 4, LiCoO 2 and LiCo 1/3Ni 1/3Mn 1/3O 2) were investigated using galvanostatic charge/discharge, electrochemical impedance Spectroscopy (EIS) and galvanostatic intermittent titration (GITT). These four electrode materials can be roughly divided into two groups according to the structure change during Li intercalation/extraction, i.e. the phase transition materials (Li 4/3Ti 5/3O 4 and LiFePO 4) and mixed phase transformation and solid solution materials (LiNi 1/3Mn 1/3Co 1/3O 2 and LiCoO 2). Both the ionic conductivity and phase transition kinetics have a strong impact on the rate capability of the electrode material in addition to the generally accepted factors such as particle size and electronic conductivity. The rate capabilities of Li 4/3Ti 5/3O 4 and LiFePO 4, which have an extended flat region in the charge/discharge curves, mainly depended on their phase transition kinetics. The rate performance of the solid solution materials were controlled by the ionic conductivity, with some influence from the electronic conductivity.

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

    NASA Astrophysics Data System (ADS)

    Dees, Dennis W.; Kawauchi, Shigehiro; Abraham, Daniel P.; Prakash, Jai

    Galvanostatic Intermittent Titration Technique (GITT) experiments were conducted to determine the lithium diffusion coefficient of LiNi 0.8Co 0.15Al 0.05O 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 -10 cm 2 s -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.

  10. 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.

  11. Influence of the morphology on the platinum electrode surface activity

    NASA Astrophysics Data System (ADS)

    Reiner, Andreas; Steiger, Beat; Scherer, Günther G.; Wokaun, Alexander

    Polycrystalline Pt electrodes with different surface characteristics were investigated by cyclic voltammetry (CV) in 0.5 M H 2SO 4. Plane electrodes showed a decrease in electrochemically active surface area while cycling in the hydrogen underpotential region (H upd), in contrast, electrodes roughened by intensive pre-cycling exhibited a stable value for the electrochemically active surface.

  12. 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. 870.2370 Section 870.2370 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is...

  13. Nickel/silicon core/shell nanosheet arrays as electrode materials for lithium ion batteries

    SciTech Connect

    Huang, X.H. Zhang, P.; Wu, J.B.; Lin, Y.; Guo, R.Q.

    2016-08-15

    Highlights: • Ni nanosheet arrays is the core and Si layer is the shell. • Ni nanosheet arrays act as a three-dimensional current collector to support Si. • Ni nanosheet arrays can improve the conductivity and stability of the electrode. • Ni/Si nanosheet arrays exhibit excellent cyclic and rate performance. - Abstract: Ni/Si core/shell nanosheet arrays are proposed to enhance the electrochemical lithium-storage properties of silicon. The arrays are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The arrays are micro-sized in height, which are constructed by interconnected Ni nanosheet as the core and Si coating layer as the shell. The electrochemical properties as anode materials of lithium ion batteries are investigated by cyclic voltammetry (CV) and galvanostatic charge-discharge tests. The arrays can achieve high reversible capacity, good cycle stability and high rate capability. It is believed that the enhanced electrochemical performance is attributed to the electrode structure, because the interconnected Ni nanosheet can act as a three-dimensional current collector, and it has the ability of improving the electrode conductivity, enlarging the electrochemical reaction interface, and suppressing the electrode pulverization.

  14. 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.

  15. 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

  16. Analysis of Long-Range Interaction in Lithium-Ion Battery Electrodes

    SciTech Connect

    Mistry, Aashutosh; Juarez-Robles, Daniel; Stein, Malcolm; Smith, Kandler; Mukherjee, Partha P.

    2016-12-01

    The lithium-ion battery (LIB) electrode represents a complex porous composite, consisting of multiple phases including active material (AM), conductive additive, and polymeric binder. This study proposes a mesoscale model to probe the effects of the cathode composition, e.g., the ratio of active material, conductive additive, and binder content, on the electrochemical properties and performance. The results reveal a complex nonmonotonic behavior in the effective electrical conductivity as the amount of conductive additive is increased. Insufficient electronic conductivity of the electrode limits the cell operation to lower currents. Once sufficient electron conduction (i.e., percolation) is achieved, the rate performance can be a strong function of ion-blockage effect and pore phase transport resistance. In conclusion, even for the same porosity, different arrangements of the solid phases may lead to notable difference in the cell performance, which highlights the need for accurate microstructural characterization and composite electrode preparation strategies.

  17. Analysis of Long-Range Interaction in Lithium-Ion Battery Electrodes

    DOE PAGES

    Mistry, Aashutosh; Juarez-Robles, Daniel; Stein, Malcolm; ...

    2016-12-01

    The lithium-ion battery (LIB) electrode represents a complex porous composite, consisting of multiple phases including active material (AM), conductive additive, and polymeric binder. This study proposes a mesoscale model to probe the effects of the cathode composition, e.g., the ratio of active material, conductive additive, and binder content, on the electrochemical properties and performance. The results reveal a complex nonmonotonic behavior in the effective electrical conductivity as the amount of conductive additive is increased. Insufficient electronic conductivity of the electrode limits the cell operation to lower currents. Once sufficient electron conduction (i.e., percolation) is achieved, the rate performance can bemore » a strong function of ion-blockage effect and pore phase transport resistance. In conclusion, even for the same porosity, different arrangements of the solid phases may lead to notable difference in the cell performance, which highlights the need for accurate microstructural characterization and composite electrode preparation strategies.« less

  18. 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

  19. A systematic investigation of polymer binder flexibility on the electrode performance of lithium-ion batteries.

    PubMed

    Yuca, Neslihan; Zhao, Hui; Song, Xiangyun; Dogdu, Murat Ferhat; Yuan, Wen; Fu, Yanbao; Battaglia, Vincent S; Xiao, Xingcheng; Liu, Gao

    2014-10-08

    The mechanical failure at the electrode interfaces (laminate/current collector and binder/particle interfaces) leads to particle isolation and delamination, which has been regarded as one of the main reasons for the capacity decay and cell failure of lithium-ion batteries (LIBs). Polymer binder provides the key function for a good interface property and for maintaining the electrode integrity of LIBs. Triethylene glycol monomethyl ether (TEG) moieties were incorporated into polymethacrylic acid (PMAA) to different extents at the molecular level. Microscratch tests of the graphite electrodes based on these binders indicate that the electrode is more flexible with 5 or 10% TEG in the polymer binders. Crack generation is inhibited by the flexible TEG-containing binder, compared to that of the unmodified PMAA-based electrode, leading to the better cycling performance of the flexible electrode. With a 10% TEG moiety in the binder, the graphite half-cell reaches a reversible capacity of >270 mAh/g at the 1C rate, compared to a value of ∼190 mAh/g for the unmodified PMAA binder.

  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.

  1. Nitrogen-Doped Porous Carbon Nanosheets from Eco-Friendly Eucalyptus Leaves as High Performance Electrode Materials for Supercapacitors and Lithium Ion Batteries.

    PubMed

    Mondal, Anjon Kumar; Kretschmer, Katja; Zhao, Yufei; Liu, Hao; Wang, Chengyin; Sun, Bing; Wang, Guoxiu

    2017-03-13

    Nitrogen-doped porous carbon nanosheets were prepared from eucalyptus tree leaves by simply mixing the leaf powders with KHCO3 and subsequent carbonisation. Porous carbon nanosheets with a high specific surface area of 2133 m(2)  g(-1) were obtained and applied as electrode materials for supercapacitors and lithium ion batteries. For supercapacitor applications, the porous carbon nanosheet electrode exhibited a supercapacitance of 372 F g(-1) at a current density of 500 mA g(-1) in 1 m H2 SO4 aqueous electrolyte and excellent cycling stability over 15 000 cycles. In organic electrolyte, the nanosheet electrode showed a specific capacitance of 71 F g(-1) at a current density of 2 Ag(-1) and stable cycling performance. When applied as the anode material for lithium ion batteries, the as-prepared porous carbon nanosheets also demonstrated a high specific capacity of 819 mA h g(-1) at a current density of 100 mA g(-1) , good rate capability, and stable cycling performance. The outstanding electrochemical performances for both supercapacitors and lithium ion batteries are derived from the large specific surface area, porous nanosheet structure and nitrogen doping effects. The strategy developed in this paper provides a novel route to utilise biomass-derived materials for low-cost energy storage systems.

  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.

  3. 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.

  4. Towards High‐Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy

    PubMed Central

    Wang, Dong; Cui, Xiaoqiang; Rojo, Teófilo

    2016-01-01

    The formation of lithium dendrites induces the notorious safety issue and poor cycling life of energy storage devices, such as lithium–sulfur and lithium–air batteries. We propose a surface energy model to describe the complex interface between the lithium anode and electrolyte. A universal strategy of hindering formation of lithium dendrites via tuning surface energy of the relevant thin film growth is suggested. The merit of the novel motif lies not only fundamentally a perfect correlation between electrochemistry and thin film fields, but also significantly promotes larger‐scale application of lithium–sulfur and lithium–air batteries, as well as other metal batteries (e.g., Zn, Na, K, Cu, Ag, and Sn). PMID:28105393

  5. 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.}

  6. Method of fabricating electrodes including high-capacity, binder-free anodes for lithium-ion batteries

    DOEpatents

    Ban, Chunmei; Wu, Zhuangchun; Dillon, Anne C.

    2017-01-10

    An electrode (110) is provided that may be used in an electrochemical device (100) such as an energy storage/discharge device, e.g., a lithium-ion battery, or an electrochromic device, e.g., a smart window. Hydrothermal techniques and vacuum filtration methods were applied to fabricate the electrode (110). The electrode (110) includes an active portion (140) that is made up of electrochemically active nanoparticles, with one embodiment utilizing 3d-transition metal oxides to provide the electrochemical capacity of the electrode (110). The active material (140) may include other electrochemical materials, such as silicon, tin, lithium manganese oxide, and lithium iron phosphate. The electrode (110) also includes a matrix or net (170) of electrically conductive nanomaterial that acts to connect and/or bind the active nanoparticles (140) such that no binder material is required in the electrode (110), which allows more active materials (140) to be included to improve energy density and other desirable characteristics of the electrode. The matrix material (170) may take the form of carbon nanotubes, such as single-wall, double-wall, and/or multi-wall nanotubes, and be provided as about 2 to 30 percent weight of the electrode (110) with the rest being the active material (140).

  7. 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.

  8. Tensor veli palatini electromyography with surface electrode applied transnasally

    PubMed Central

    Picciotti, PM; Della Marca, G; Restuccia, D; Rigante, M; Di Nardo, W; Scarano, E

    2005-01-01

    Summary A new technique is proposed for paratubal electromyography, using a surface, non-invasive, electrode applied transnasally under nasopharyngoscope guidance. This electrode records activity of the tensor veli palatini muscle during swallowing. This technique is of interest for two reasons: endoscopic guid-ance offers the possibility to check correct positioning of the electrode recording at tensor veli palatini muscle level. Introduction of the non-invasive surface electrode is simple and not painful. PMID:16116836

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

    DOE PAGES

    Barai, Pallab; Smith, Kandler; Chen, Chien -Fan; ...

    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

  10. 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.

  11. 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

  12. Complexity and Fermi surface deformation in compressed lithium

    NASA Astrophysics Data System (ADS)

    Rodriguez-Prieto, A.; Bergara, A.; Silkin, V. M.; Echenique, P. M.

    2006-11-01

    Recently reported structural complexity and enhanced temperature superconducting transitions in lithium under pressure have increased the interest in light alkalies, otherwise considered as simple and well-known systems under normal conditions. Here we present an analysis of the pressure-induced Fermi surface deformation in lithium and its relation to the observed complexity. According to our calculations, the Fermi surface becomes increasingly anisotropic with pressure and at 8GPa contacts the Brillouin zone boundary inducing a Hume-Rothery mechanism explaining the bcc-fcc transition. Around 30GPa increasing cooper-like necks and an extended nesting are observed in the Fermi surface in the fcc phase, enhancing the electronic susceptibility response function and inducing a strong phonon softening. This softening, besides preluding the transition to complex structures and providing a better understanding of the observed superconductivity, is expected to induce other yet unexplored anomalies in compressed lithium.

  13. 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.

  14. Effects of lithium content on the electrochemical lithium intercalation reaction into LiNiO 2 and LiCoO 2 electrodes

    NASA Astrophysics Data System (ADS)

    Choi, Young-Min; Pyun, Su-Il; Bae, Joon-Sung; Moon, Seong-In

    The electrochemical lithium intercalation reaction into LiNiO 2 and LiCoO 2 electrodes in 1 M LiClO 4—propylene carbonate solution is investigated as a function of lithium content in the oxide electrodes by using X-ray diffractometry (XRD), electrochemical impedance spectroscopy (EIS), and a galvanostatic intermittent titration technique (GITT). Li 1-δNiO 2 shows a greater loss in capacity during the first intermittent discharge, as well as a higher resistance for the electrochemical intercalation reaction, in comparison with Li 1-δCoO 2. This is attributed to a partial cation mixing in Li 1-δNiO 2 which is substantiated by XRD studies. The electrochemical impedance spectra of the Li 1-δNiO 2 electrode reveals that the magnitude of the intermediate frequency arc that is associated with the absorption reaction decreases with increasing lithium content, (1 — δ), in the range from 0.5 to 0.7. By contrast, Li 1-δCoO 2 exhibits the reverse behaviour.—The component diffusivities of lithium ions display a nearly constant value, in the order of 10 -11 cm 2 s -1, for both electrodes at room temperature, irrespective of the value of (1 — δ) over the range 0.5-0.7. It is suggested that lithium-ion diffusion through both the layered oxides is affected by the number of empty sites within the lithium-ion layer, and not by the lattice parameter.

  15. 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.

  16. SnO2@PANI Core-Shell Nanorod Arrays on 3D Graphite Foam: A High-Performance Integrated Electrode for Lithium-Ion Batteries.

    PubMed

    Zhang, Feng; Yang, Chengkai; Gao, Xin; Chen, Shuai; Hu, Yiran; Guan, Huanqin; Ma, Yurong; Zhang, Jin; Zhou, Henghui; Qi, Limin

    2017-03-22

    The rational design and controllable fabrication of electrode materials with tailored structures and superior performance is highly desirable for the next-generation lithium ion batteries (LIBs). In this work, a novel three-dimensional (3D) graphite foam (GF)@SnO2 nanorod arrays (NRAs)@polyaniline (PANI) hybrid architecture was constructed via solvothermal growth followed by electrochemical deposition. Aligned SnO2 NRAs were uniformly grown on the surface of GF, and a PANI shell with a thickness of ∼40 nm was coated on individual SnO2 nanorods, forming a SnO2@PANI core-shell structure. Benefiting from the synergetic effect of 3D GF with large surface area and high conductivity, SnO2 NRAs offering direct pathways for electrons and lithium ions, and the conductive PANI shell that accommodates the large volume variation of SnO2, the binder-free, integrated GF@SnO2 NRAs@PANI electrode for LIBs exhibited high capacity, excellent rate capability, and good electrochemical stability. A high discharge capacity of 540 mAh g(-1) (calculated by the total mass of the electrode) was achieved after 50 cycles at a current density of 500 mA g(-1). Moreover, the electrode demonstrated superior rate performance with a discharge capacity of 414 mAh g(-1) at a high rate of 3 A g(-1).

  17. A Tunable 3D Nanostructured Conductive Gel Framework Electrode for High-Performance Lithium Ion Batteries.

    PubMed

    Shi, Ye; Zhang, Jun; Bruck, Andrea M; Zhang, Yiman; Li, Jing; Stach, Eric A; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S; Yu, Guihua

    2017-03-22

    This study develops a tunable 3D nanostructured conductive gel framework as both binder and conductive framework for lithium ion batteries. A 3D nanostructured gel framework with continuous electron pathways can provide hierarchical pores for ion transport and form uniform coatings on each active particle against aggregation. The hybrid gel electrodes based on a polypyrrole gel framework and Fe3 O4 nanoparticles as a model system in this study demonstrate the best rate performance, the highest achieved mass ratio of active materials, and the highest achieved specific capacities when considering total electrode mass, compared to current literature. This 3D nanostructured gel-based framework represents a powerful platform for various electrochemically active materials to enable the next-generation high-energy batteries.

  18. Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

    PubMed

    Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

    2013-07-23

    Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

  19. Aluminum-doped lithium nickel cobalt oxide electrodes for high-power lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, C. H.; Liu, J.; Stoll, M. E.; Henriksen, G.; Vissers, D. R.; Amine, K.

    Non-doped and aluminum-doped LiNi 0.8Co 0.2O 2 cathodes from three industrial developers coupled with graphite anodes were made into lithium-ion cells for high-power applications. The powder morphology of the active cathode materials was examined by a scanning electron microscope. The electrochemical performance of these cells was investigated by hybrid pulse power characterization (HPPC) testing, accelerated aging, and AC impedance measurement of symmetric cells. Although all of the fresh cells are found to meet and exceed the power requirements set by PNGV, the power capability of those cells with non-doped LiNi 0.8Co 0.2O 2 cathodes fades rapidly due to the rise of the cell impedance. Al-doping is found very effective to suppress the cell impedance rise by stabilizing the charge-transfer impedance on the cathode side. The stabilization mechanism may be related to the low average oxidation state of nickel ions in the cathode. The powder morphology also plays a secondary role in determining the impedance stabilization.

  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. Study on the Effect of the Three-Dimensional Electrode in Degradation of Methylene Blue by Lithium Modified Rectorite

    PubMed Central

    Huang, Jian; Du, Ying; Wang, Yingru; Wang, Ci'en

    2016-01-01

    This study presents the electrochemical degradation of methylene blue (MB) wastewater in a synthetic solution using three-dimensional particle electrodes. The novel particle electrodes were fabricated in this work using the lithium modified rectorite (Li-REC). The adsorption property of the fabricated particle electrodes was studied in a series of experiments. The optimum electrochemical operating conditions of plate distance, cell voltage, and concentration of electrolyte were 2 cm, 9 V, and 0.06 mol L−1, respectively. It was also found that microwave irradiation can effectively improve the adsorption property and electrical property of the fabricated electrodes. In addition, the scanning electron microscope (SEM) of the fabricated electrodes was investigated. The experimental results revealed the order of adsorption property and electrical property of the fabricated electrodes. So, fabricated electrodes are not only of low cost and mass produced, but also efficient to achieve decolorization of MB solution. PMID:27974993

  2. Study on the Effect of the Three-Dimensional Electrode in Degradation of Methylene Blue by Lithium Modified Rectorite.

    PubMed

    Huang, Jian; Ming, Yin'an; Du, Ying; Wang, Yingru; Wang, Ci'en

    2016-01-01

    This study presents the electrochemical degradation of methylene blue (MB) wastewater in a synthetic solution using three-dimensional particle electrodes. The novel particle electrodes were fabricated in this work using the lithium modified rectorite (Li-REC). The adsorption property of the fabricated particle electrodes was studied in a series of experiments. The optimum electrochemical operating conditions of plate distance, cell voltage, and concentration of electrolyte were 2 cm, 9 V, and 0.06 mol L(-1), respectively. It was also found that microwave irradiation can effectively improve the adsorption property and electrical property of the fabricated electrodes. In addition, the scanning electron microscope (SEM) of the fabricated electrodes was investigated. The experimental results revealed the order of adsorption property and electrical property of the fabricated electrodes. So, fabricated electrodes are not only of low cost and mass produced, but also efficient to achieve decolorization of MB solution.

  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. 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.

  5. 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.

  6. 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.

  7. Modulated Surface Vibrational Spectroscopies at Electrode/Electrolyte Interfaces.

    DTIC Science & Technology

    1984-11-28

    methanol, formaldehyde, or formic acid . Figure 8 gives examples of the spectra obtained from a poisoned electrode for the system platinum/formaldehyde...reflection losses at the atmosphere /window interface allowing more of the radiation to be utilized at the solution/electrode interface. More details on the... catalysis at electrode surfaces. * . ~ . . *~~ . . . . . . . . ’ . . . . .. . . . . . . . . .j

  8. Highly Ordered Mesostructured Vanadium Phosphonate toward Electrode Materials for Lithium-Ion Batteries.

    PubMed

    Mei, Peng; Pramanik, Malay; Lee, Jaewoo; Ide, Yusuke; Alothman, Zeid Abdullah; Kim, Jung Ho; Yamauchi, Yusuke

    2017-03-28

    Highly ordered mesostructured vanadium phosphonates (VP) have been synthesized in the presence of cetyltrimethylammonium bromide (CTAB) as a structure-directing agent. Nitrilotris(methylene)triphosphonic acid (NMPA) and (ammonium/sodium) metavanadate (NH4 VO3 /NaVO3 ) have been used for the construction of pore walls. The CTAB templates are removed from the materials by an extraction process without destroying the parent mesostructure. The formation mechanism for the ordered mesoporous structure and its impact on electrochemical application in lithium ion batteries (LIBs) are explained by considering the structural and electrochemical stability of the framework. The results demonstrate that the counter cations (NH4(+) /Na(+) ) of the metavanadate precursors have a crucial role in stabilizing the mesoporous structure of the mesoporous VP materials. Mesoporous VP materials with highly ordered structure have great applicability as high-performance electrode materials in LIBs due to the advantages of their large contact area with electrolyte and short transport paths for lithium ions. Mesoporous VP electrodes exhibit high reversible specific capacity with superb cycling stability (100 cycles) and excellent retention of capacity (92 %).

  9. 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.

  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. Cryogenic surface-electrode ion trap apparatus

    NASA Astrophysics Data System (ADS)

    Dubielzig, Timko; Carsjens, Martina; Kohnen, Matthias; Grondkowski, Sebastian; Ospelkaus, Christian

    2014-05-01

    In this talk we describe the infrastructure necessary to operate a surface-electrode ion trap with integrated microwave conductors for near-field quantum control of 9Be+ in a cryogenic environment. These traps are promising systems for analog quantum simulators and for quantum logic applications. Our group recently developed a trap with an integrated meander-like microwave guide for driving motional sidebands on an 9Be+ ion. The trap will be operated in a cryogenic vacuum chamber. We will discuss the vibrational isolated closed cycle cryostat and the design of the vacuum chamber with all electrical supplies necessary to apply two different microwave currents, dc voltages and three independent rf supplies to generate a reconfigurable rf trapping potential. We will also discuss the used hyperfine qubit and the laser systems required to cool and repump. Furthermore we will present the cryogenic, high aperture and fully acromatic imaging system.

  12. Development of lithium powder based anode with conductive carbon materials for lithium batteries

    NASA Astrophysics Data System (ADS)

    Park, Man Su

    Current lithium ion battery with a graphite anode shows stable cycle performance and safety. However, the lithium ion battery still has the limitation of having a low energy density caused by the application of lithium intercalated cathode and anode with low energy density. The combination of high capacity non-lithiated cathode such as sulfur and carbon and lithium metal anode has been researched for a long time to maximize battery's energy density. However, this cell design also has a lot of technical challenges to be solved. Among the challenges, lithium anode's problem related to lithium dendrite growth causing internal short and low cycling efficiency is very serious. Thus, extensive research on lithium metal anode has been performed to solve the lithium dendrite problem and a major part of the research has been focused on the control of the interface between lithium and electrolyte. However, research on lithium anode design itself has not been much conducted. In this research, innovative lithium anode design for less dendrite growth and higher cycling efficiency was suggested. Literature review for the lithium dendrite growth mechanism was conducted in Chapter 2 to develop electrode design concept and the importance of the current density on lithium dendrite growth was also found in the literatures. The preliminary test was conducted to verify the developed electrode concept by using lithium powder based anode (LIP) with conductive carbon materials and the results showed that lithium dendrite growth could be suppressed in this electrode design due to its increased electrochemical surface area and lithium deposition sites during lithium deposition. The electrode design suggested in Chapter 2 was extensively studied in Chapter 3 in terms of lithium dendrite growth morphology, lithium cycling efficiency and full cell cycling performance. This electrode concept was further developed to maximize the electrode's performance and safety in Chapter 4. In this new

  13. 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.

  14. 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

  15. The Importance of Detecting Lithium on the Surface of Mars

    NASA Astrophysics Data System (ADS)

    Heredia, A.; Colín-García, M.; Valdivia Silva, J.; Beraldi, H.; Negrón-Mendoza, A.; Durand-Manterola, H.; García-Martínez, J. L.; Ramos, S.; Ortega, F.

    2012-09-01

    Lithium (Li) is the third element of the periodic table and was created in the Big Bang together with hydrogen and helium. In water solution it exhibits low vapor pressure and freezing point, and other colligative properties enhancing the range of liquid water availability. With organic compounds, it forms organo-lithium reagents with direct covalent bond allowing for organic complexity. Lithium accreted with the Sun and planets in minor amounts and later it originated by nuclear fission processes due to highenergy cosmic rays. Here, we suggest that detecting Li in the surface of Mars by instruments bound to Curiosity rover may provide crucial evidence for the potential chemical evolution in the red planet in the presence of liquid water.

  16. 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

  17. Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design [Morphological design of silicon electrode with anisotropic interface reaction rate for lithium ion batteries

    SciTech Connect

    An, Yonghao; Wood, Brandon C.; Ye, Jianchao; Chiang, Yet -Ming; Wang, Y. Morris; Tang, Ming; Jiang, Hanqing

    2015-06-08

    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. In conclusion, 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.

  18. Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design [Morphological design of silicon electrode with anisotropic interface reaction rate for lithium ion batteries

    DOE PAGES

    An, Yonghao; Wood, Brandon C.; Ye, Jianchao; ...

    2015-06-08

    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 counteractmore » 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. In conclusion, 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.« less

  19. 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.

  20. 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.

  1. In situ micro-FTIR study of the solid-solid interface between lithium electrode and polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Cheng, H.; Zhu, C. B.; Lu, M.; Yang, Y.

    In situ micro-FTIR spectroscopy was explored to characterize the solid-solid interface between lithium electrode and polymer electrolytes. The cyclic voltammetric (CV) results indicated that the reduction reactions of oxygen and water as well as the formation of underpotential deposition (UPD) Li occur in the Li/PEO 20-LiN(CF 3SO 2) 2 electrolyte interface in the different potential region. The infrared spectral changes observed during the CV process revealed that there is a direct correlation between the CV peaks and the magnitude of the infrared peaks. It is shown that the infrared reflectivity from the solid-solid interface is very sensitive to the formation of the passive layer on the lithium electrodes. The results obtained from optical micrographs also displayed directly the formation of the passive layer along with lithium deposition and dissolution process. It is correlated well with in situ FTIR and electrochemical experiments.

  2. A novel mechanistic modeling framework for analysis of electrode balancing and degradation modes in commercial lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Schindler, Stefan; Danzer, Michael A.

    2017-03-01

    Aiming at a long-term stable and safe operation of rechargeable lithium-ion cells, elementary design aspects and degradation phenomena have to be considered depending on the specific application. Among the degrees of freedom in cell design, electrode balancing is of particular interest and has a distinct effect on useable capacity and voltage range. Concerning intrinsic degradation modes, understanding the underlying electrochemical processes and tracing the overall degradation history are the most crucial tasks. In this study, a model-based, minimal parameter framework for combined elucidation of electrode balancing and degradation pathways in commercial lithium-ion cells is introduced. The framework rests upon the simulation of full cell voltage profiles from the superposition of equivalent, artificially degraded half-cell profiles and allows to separate aging contributions from loss of available lithium and active materials in both electrodes. A physically meaningful coupling between thermodynamic and kinetic degradation modes based on the correlation between altered impedance features and loss of available lithium as well as loss of active material is proposed and validated by a low temperature degradation profile examined in one of our recent publications. The coupled framework is able to determine the electrode balancing within an error range of < 1% and the projected cell degradation is qualitatively and quantitatively in line with experimental observations.

  3. 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.

  4. 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

  5. Surface Engineering and Design Strategy for Surface-Amorphized TiO2@Graphene Hybrids for High Power Li-Ion Battery Electrodes.

    PubMed

    Zhou, Tengfei; Zheng, Yang; Gao, Hong; Min, Shudi; Li, Sean; Liu, Hua Kun; Guo, Zaiping

    2015-09-01

    Surface amorphization provides unprecedented opportunities for altering and tuning material properties. Surface-amorphized TiO2@graphene synthesized using a designed low temperature-phase transformation technique exhibits significantly improved rate capability compared to well-crystallized TiO2@graphene and bare TiO2 electrodes. These improvements facilitates lithium-ion transport in both insertion and extraction processes and enhance electrolyte absorption capability.

  6. 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.

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

    PubMed

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

    2015-11-26

    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).

  8. Nanoscale imaging of lithium ion distribution during in situ operation of battery electrode and electrolyte.

    PubMed

    Holtz, Megan E; Yu, Yingchao; Gunceler, Deniz; Gao, Jie; Sundararaman, Ravishankar; Schwarz, Kathleen A; Arias, Tomás A; Abruña, Héctor D; Muller, David A

    2014-03-12

    A major challenge in the development of new battery materials is understanding their fundamental mechanisms of operation and degradation. Their microscopically inhomogeneous nature calls for characterization tools that provide operando and localized information from individual grains and particles. Here, we describe an approach that enables imaging the nanoscale distribution of ions during electrochemical charging of a battery in a transmission electron microscope liquid flow cell. We use valence energy-loss spectroscopy to track both solvated and intercalated ions, with electronic structure fingerprints of the solvated ions identified using an ab initio nonlinear response theory. Equipped with the new electrochemical cell holder, nanoscale spectroscopy and theory, we have been able to determine the lithiation state of a LiFePO4 electrode and surrounding aqueous electrolyte in real time with nanoscale resolution during electrochemical charge and discharge. We follow lithium transfer between electrode and electrolyte and image charging dynamics in the cathode. We observe competing delithiation mechanisms such as core-shell and anisotropic growth occurring in parallel for different particles under the same conditions. This technique represents a general approach for the operando nanoscale imaging of electrochemically active ions in the electrode and electrolyte in a wide range of electrical energy storage systems.

  9. 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.

  10. Biomimetic Ant-Nest Electrode Structures for High Sulfur Ratio Lithium-Sulfur Batteries.

    PubMed

    Ai, Guo; Dai, Yiling; Mao, Wenfeng; Zhao, Hui; Fu, Yanbao; Song, Xiangyun; En, Yunfei; Battaglia, Vincent S; Srinivasan, Venkat; Liu, Gao

    2016-09-14

    The lithium-sulfur (Li-S) rechargeable battery has the benefit of high gravimetric energy density and low cost. Significant research currently focuses on increasing the sulfur loading and sulfur/inactive-materials ratio, to improve life and capacity. Inspired by nature's ant-nest structure, this research results in a novel Li-S electrode that is designed to meet both goals. With only three simple manufacturing-friendly steps, which include slurry ball-milling, doctor-blade-based laminate casting, and the use of the sacrificial method with water to dissolve away table salt, the ant-nest design has been successfully recreated in an Li-S electrode. The efficient capabilities of the ant-nest structure are adopted to facilitate fast ion transportation, sustain polysulfide dissolution, and assist efficient precipitation. High cycling stability in the Li-S batteries, for practical applications, has been achieved with up to 3 mg·cm(-2) sulfur loading. Li-S electrodes with up to a 85% sulfur ratio have also been achieved for the efficient design of this novel ant-nest structure.

  11. 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

    2016-03-02

    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.

  12. 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.

  13. 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

    2016-03-02

    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.

  14. 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.

  15. 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.

  16. Detecting Skin Burns Induced by Surface Electrodes

    DTIC Science & Technology

    2007-11-02

    density image were taken, the electrode peeled off the skin, and a photograph taken to complete the post-burn dataset. Finally, the used electrodes were...suggesting the breakdown of the barrier layer capacitance in the skin epidermis . Line monitoring of the skin impedance can predict the onset of the burns

  17. Confinement of reaction components at electrode surface

    DOEpatents

    Luca, Oana R.; Weitekamp, Raymond; Grubbs, Robert H.; Atwater, Harry A.; Mitrovic, Slobodan

    2017-03-14

    A CO.sub.2 reduction electrode includes an active layer on an electrode base. The active layer includes a polymer that includes one or more reaction components selected from a group consisting of a CO.sub.2 reduction catalyst and an activator that bonds CO.sub.2 so as to form a CO.sub.2 reduction intermediate.

  18. 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.

  19. 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.

  20. 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.

  1. Silicon micropowder negative electrode endures more than 1000 cycles when a surface-roughened clad current collector is used

    NASA Astrophysics Data System (ADS)

    Kataoka, Riki; Oda, Yoshimitsu; Inoue, Ryouji; Kawasaki, Norioki; Takeichi, Nobuhiko; Kiyobayashi, Tetsu

    2017-04-01

    A surface-roughened clad (S-clad) current collector significantly extends the cycle-life of the lithium ion negative electrode composed of a silicon micropowder and an aqueous binder. The high tensile strength of the S-clad is also proved to be important for improving the battery performance of the electrode by comparison to a surface-roughened pure Cu current collector. Moreover, adding 10 vol.% fluoroethylene carbonate to the electrolyte further extends the cycle-life of the Si electrode. The synergic effect of the high adhesive and tensile strength of the S-clad current collector as well as the electrolyte additive results in maintaining the reversible capacity of 1000 mA h g-1 for more than 1000 cycles, in which 1.0-1.2 mg cm-2 of the active material is loaded on the electrode.

  2. 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.

  3. Electrode structure and method for making the same

    DOEpatents

    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.

  4. 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.

  5. 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.

  6. A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries.

    PubMed

    Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E C; Matic, Aleksandar

    2016-12-23

    Societies' increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of "no battery without binder" and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm(2) after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

  7. A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

    PubMed Central

    Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

    2016-01-01

    Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3–5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications. PMID:28008981

  8. A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

    2016-12-01

    Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3–5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

  9. 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.

  10. 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.

  11. 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.

  12. Origin of additional capacities in metal oxide lithium-ion battery electrodes.

    PubMed

    Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan; Borkiewicz, Olaf J; Cheng, Jun; Hua, Xiao; Dunstan, Matthew T; Yu, Xiqian; Wiaderek, Kamila M; Du, Lin-Shu; Chapman, Karena W; Chupas, Peter J; Yang, Xiao-Qing; Grey, Clare P

    2013-12-01

    Metal fluorides/oxides (MF(x)/M(x)O(y)) are promising electrodes for lithium-ion batteries that operate through conversion reactions. These reactions are associated with much higher energy densities than intercalation reactions. The fluorides/oxides also exhibit additional reversible capacity beyond their theoretical capacity through mechanisms that are still poorly understood, in part owing to the difficulty in characterizing structure at the nanoscale, particularly at buried interfaces. This study employs high-resolution multinuclear/multidimensional solid-state NMR techniques, with in situ synchrotron-based techniques, to study the prototype conversion material RuO2. The experiments, together with theoretical calculations, show that a major contribution to the extra capacity in this system is due to the generation of LiOH and its subsequent reversible reaction with Li to form Li2O and LiH. The research demonstrates a protocol for studying the structure and spatial proximities of nanostructures formed in this system, including the amorphous solid electrolyte interphase that grows on battery electrodes.

  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. CNT Sheet Air Electrode for the Development of Ultra-High Cell Capacity in Lithium-Air Batteries

    PubMed Central

    Nomura, Akihiro; Ito, Kimihiko; Kubo, Yoshimi

    2017-01-01

    Lithium-air batteries (LABs) are expected to provide a cell with a much higher capacity than ever attained before, but their prototype cells present a limited areal cell capacity of no more than 10 mAh cm−2, mainly due to the limitation of their air electrodes. Here, we demonstrate the use of flexible carbon nanotube (CNT) sheets as a promising air electrode for developing ultra-high capacity in LAB cells, achieving areal cell capacities of up to 30 mAh cm−2, which is approximately 15 times higher than the capacity of cells with lithium-ion battery (LiB) technology (~2 mAh cm−2). During discharge, the CNT sheet electrode experienced enormous swelling to a thickness of a few millimeters because of the discharge product deposition of lithium peroxide (Li2O2), but the sheet was fully recovered after being fully charged. This behavior results from the CNT sheet characteristics of the flexible and fibrous conductive network and suggests that the CNT sheet is an effective air electrode material for developing a commercially available LAB cell with an ultra-high cell capacity. PMID:28378746

  15. 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.

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

    DOE PAGES

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

    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

  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. Experimental studies of lithium-based surface chemistry for fusion plasma-facing materials applications

    NASA Astrophysics Data System (ADS)

    Allain, J. P.; Rokusek, D. L.; Harilal, S. S.; Nieto-Perez, M.; Skinner, C. H.; Kugel, H. W.; Heim, B.; Kaita, R.; Majeski, R.

    2009-06-01

    Lithium has enhanced the operational performance of fusion devices such as: TFTR, CDX-U, FTU, T-11 M, and NSTX. Lithium in the solid and liquid state has been studied extensively in laboratory experiments including its erosion and hydrogen-retaining properties. Reductions in physical sputtering up to 40-60% have been measured for deuterated solid and liquid lithium surfaces. Computational modeling indicates that up to a 1:1 deuterium volumetric retention in lithium is possible. This paper presents the results of systematic in situ laboratory experimental studies on the surface chemistry evolution of ATJ graphite under lithium deposition. Results are compared to post-mortem analysis of similar lithium surface coatings on graphite exposed to deuterium discharge plasmas in NSTX. Lithium coatings on plasma-facing components in NSTX have shown substantial reduction of hydrogenic recycling. Questions remain on the role lithium surface chemistry on a graphite substrate has on particle sputtering (physical and chemical) as well as hydrogen isotope recycling. This is particularly due to the lack of in situ measurements of plasma-surface interactions in tokamaks such as NSTX. Results suggest that the lithium bonding state on ATJ graphite is lithium peroxide and with sufficient exposure to ambient air conditions, lithium carbonate is generated. Correlation between both results is used to assess the role of lithium chemistry on the state of lithium bonding and implications on hydrogen pumping and lithium sputtering. In addition, reduction of factors between 10 and 30 reduction in physical sputtering from lithiated graphite compared to pure lithium or carbon is also measured.

  19. 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.

  20. 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.

  1. Influence of the structure of the anion in an ionic liquid electrolyte on the electrochemical performance of a silicon negative electrode for a lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Kazuki; Domi, Yasuhiro; Usui, Hiroyuki; Shimizu, Masahiro; Matsumoto, Kuninobu; Nokami, Toshiki; Itoh, Toshiyuki; Sakaguchi, Hiroki

    2017-01-01

    We investigated the influence of the anions in ionic liquid electrolytes on the electrochemical performance of a silicon (Si) negative electrode for a lithium-ion battery. While the electrode exhibited poor cycle stability in tetrafluoroborate-based and propylene carbonate-based electrolytes, better cycle performance was achieved in bis(fluorosulfonyl)amide (FSA-)- and bis(trifluoromethanesulfonyl)amide (TFSA-)-based electrolytes, in which the discharge capacity of a Si electrode was more than 1000 mA h g-1 at the 100th cycle. It is considered that a surface film derived from FSA-- and TFSA--based electrolytes effectively suppressed continuous decomposition of the electrolyte. In a capacity limitation test, a discharge capacity of 1000 mA h g-1 was maintained even after about the 1600th cycle in the FSA--based electrolyte, which corresponds to a cycle life almost twice as long as that in TFSA--based electrolyte. This result should be explained by the high structural stability of FSA--derived surface film. In addition, better rate capability with a discharge capacity of 700 mA h g-1 was obtained at a high current rate of 6 C (21 A g-1) in FSA--based electrolyte, which was 7-fold higher than that in TFSA--based electrolyte. These results clarified that FSA--based ionic liquid electrolyte is the most promising candidate for Si-based negative electrodes.

  2. 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.

  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. 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.

  5. Cyclopentadithiophene-benzoic acid copolymers as conductive binders for silicon nanoparticles in anode electrodes of lithium ion batteries.

    PubMed

    Wang, Kuo-Lung; Kuo, Tzu-Husan; Yao, Chun-Feng; Chang, Shu-Wei; Yang, Yu-Shuo; Huang, Hsin-Kai; Tsai, Cho-Jen; Horie, Masaki

    2017-02-02

    Cyclopentadithiophene and methyl-2,5-dibromobenzoate have been copolymerised via palladium complex catalysed direct arylation. The methyl ester group in the benzoate unit is converted to the carboxyl group via saponification. The polymers are mixed with Si nanoparticles for use as conducting binders in the fabrication of an anode electrode in lithium ion batteries. The battery with the electrode incorporating the saponified polymer shows much higher specific capacity of up to 1820 mA h g(-1) (total weight) and a higher stability compared with the battery including the polymer before the saponification.

  6. 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

  7. One Step Synthesis of Uniform SnO2 Electrode by UV Curing Technology toward Enhanced Lithium-Ion Storage.

    PubMed

    Wei, Hang; Xia, Zhonghong; Xia, Dingguo

    2017-03-01

    A uniform anode material composed of ultrasmall tin oxide (SnO2) nanoparticles with an excellent lithium-ion (Li-ion) storage performance is obtained for the first time through one step UV curing technology. The diameter of ∼3 nm-sized SnO2 particles is uniformly dispersed in the styrylpyridinium (SbQ) polymer because of its photo-cross-linking property. The in situ cross-linking of SbQ polymer not only assist synthesis of uniform ultrasmall SnO2, but act as a strong adhesion binder on SnO2 nanoparticles, thereby effectively accommodating the volume expansion of SnO2 anodes during cycling process. The uniform electrode exhibits substantially higher specific capacity and longer cycling stability compared with the SnO2 nanoparticles electrodes treated by traditional PVDF-mixing method. A stable specific capacity of 572.5 mA h g(-1) of the SnO2 electrode derived from UV curing technology is obtained at a current density of 0.2 C (156.2 mA g(-1)) after 150 cycles. Even at high rate of 5 C (3905 mA g(-1)), the electrode still demonstrates specific capacity of 440.2 mA h g(-1). Therefore, the scalable and low-cost synthetic approach described herein can readily be extended to other nanomaterials electrodes to improve their lithium-storage properties.

  8. Engineering hybrid nanostructures of active materials: Applications as electrode materials in lithium ion rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Huang, Huan

    Aiming to significantly improve the electrochemical properties of electroactive materials for lithium ion batteries, three novel hybrid nanostructures were developed in this thesis. These include nanostructure A: V2O 5 coated on polymer electrolyte-grafted carbon black, nanostructure B: electrode materials incorporated into an electronically conductive carbon web, and nanostructure C: electrode materials dispersed in a conductive porous carbon matrix. Nanocomposites possessing nanostructure A are fast electronic and ionic transport materials. The improved kinetic properties are due to the incorporated carbon core and the grafted polymer electrolyte in the unique structure. The V2O5 xerogel coated polymer electrolyte-grafted carbon blacks, or V2O5/C-PEG, can reach a capacity as high as 320 mAh/g, and exhibit outstanding rate sustainability (e.g. 190 mAh/g at 14C). This class of nanostructured composites is promising for high power/current applications. Nanostructure B was extremely successful when applied to very poorly conductive active materials, such as LiFePO4 and Li3V 2(PO4)3. In this nanostructure, the web-like carbon framework not only supplies a facile electron transport path, but also provides excellent electronic contact between carbon and the insulating active materials. At room temperature, the LiFePO4/C nanocomposite successfully reaches almost full capacity, along with greatly improved rate sustainability and excellent cycling stability. At elevated temperatures (e.g. 40°C and 60°C), the full capacity is readily accessible over a wide rate range, even at a very fast rate of 2C or 5C. The Li3V2(PO4) 3/C nanocomposite can extract all three lithium in the formula at a rate of 1C, resulting in a high capacity of 200 mAh/g. Therefore, through designing hybrid nanostructures with nanostructure B, we can make insulating active materials into good cathode materials. Nanostructure C was employed for Sn-based anode materials, in order to improve their cycling

  9. A simple technique for measuring the fracture energy of lithiated thin-film silicon electrodes at various lithium concentrations

    NASA Astrophysics Data System (ADS)

    Choi, Yong Seok; Pharr, Matt; Oh, Kyu Hwan; Vlassak, Joost J.

    2015-10-01

    We have measured the fracture energy of lithiated silicon thin-film electrodes as a function of lithium concentration using a bending test. First, silicon thin-films on copper substrates were lithiated to various states of charge. Then, bending tests were performed by deforming the substrate to a pre-defined shape, producing a variation of the curvature along the length of the electrode. The bending tests allow determination of the critical strains at which cracks initiate in the lithiated silicon. Using the substrate curvature technique, we also measured the elastic moduli and the stresses that develop in the electrodes during electrochemical lithiation. From these measurements, the fracture energy was calculated as a function of lithium concentration using a finite element simulation of fracture of an elastic film on an elastic-plastic substrate. The fracture energy was determined to be Γ = 12.0 ± 3.0 J m-2 for amorphous silicon and Γ = 10.0 ± 3.6 J m-2 for Li3.28Si, with little variation in the fracture energy for intermediate Li concentrations. These results provide a guideline for the practical design of high-capacity lithium ion batteries to avoid fracture. The experimental technique described in this paper also provides a simple means of measuring the fracture energy of brittle thin-films.

  10. 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

    2014-07-16

    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.

  11. Surface film formation on nickel electrodes in a propylene carbonate solution at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Mogi, Ryo; Inaba, Minoru; Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi

    The effect of temperature on surface film formation on nickel electrode was studied in 1 mol dm -3 bis(perfluoroethylsulfonyl)imide dissolved in propylene carbonate by atomic force microscopy (AFM) and ac impedance spectroscopy. Cyclic voltammetry measurements revealed that electrolyte decomposition reactions are accelerated at elevated temperatures, especially at 60 and 80 °C. In situ AFM measurements showed that the film formation is fast and the resulting surface film is thicker at 80 °C than at room temperature. Furthermore, it was confirmed by ac impedance measurements that the resistance of surface film was very low at elevated temperatures. These results were discussed in relation to superior cycling characteristics of lithium deposition and dissolution at the elevated temperatures.

  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. 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 NiCo2O4 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 NiCo2O4 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 NiCo2O4 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 NiCo2O4. 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 NiCo2O4 coated 3D graphene structure. The simple preparation process and easily controllable morphology make the binder-free NiCo2O4/3D-GNF hybrid a potential material for commercial applications.

  14. A microwave synthesis of mesoporous NiCo2O4 nanosheets as electrode materials for lithium-ion batteries and supercapacitors.

    PubMed

    Mondal, Anjon Kumar; Su, Dawei; Chen, Shuangqiang; Kretschmer, Katja; Xie, Xiuqiang; Ahn, Hyo-Jun; Wang, Guoxiu

    2015-01-12

    A facile microwave method was employed to synthesize NiCo2 O4 nanosheets as electrode materials for lithium-ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller methods. Owing to the porous nanosheet structure, the NiCo2 O4 electrodes exhibited a high reversible capacity of 891 mA h g(-1) at a current density of 100 mA g(-1) , good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo2 O4 nanosheets demonstrated a specific capacitance of 400 F g(-1) at a current density of 20 A g(-1) and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode-electrolyte contact area and facilitate rapid ion transport.

  15. 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 ...

  16. TiO 2-B nanowires as negative electrodes for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Armstrong, A. Robert; Armstrong, Graham; Canales, Jesus; Bruce, Peter G.

    TiO 2-B nanowires (20-40 nm diameter) may be prepared in high yield by a simple synthetic procedure. Lithium may be intercalated up to Li 0.91TiO 2-B corresponding to a capacity of 305 mAh g -1 and at a potential of 1.6 V versus Li + (1 M)/Li. This can be compared with 160 mAh g -1 for Li 4Ti 5O 12 and 165 mAh g -1 for TiO 2-anatase. Following a small irreversible capacity on the first cycle, capacity retention is excellent corresponding to a fade of <0.1% per cycle at a rate of 50 mA g -1. A capacity of 160 mAh g -1 is sustained at a rate of 500 mA g -1 in electrodes that were not optimised for rate capability. Results to date indicate that the small irreversible loss of capacity on the first cycle is not associated with a SEI layer.

  17. 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

  18. Electrochemical performance and kinetic behavior of lithium ion in Li4Ti5O12 thin film electrodes

    NASA Astrophysics Data System (ADS)

    Deng, Jianqiu; Lu, Zhouguang; Chung, C. Y.; Han, Xiaodong; Wang, Zhongmin; Zhou, Huaiying

    2014-09-01

    Li4Ti5O12 thin film electrodes are successfully deposited on Pt/Ti/SiO2/Si substrates by pulsed laser deposition (PLD) technique. The microstructure and morphology of Li4Ti5O12 thin films are characterized by XRD and ESEM. The electrochemical properties of Li4Ti5O12 thin film electrodes are evaluated by galvanostatic cycling test. The kinetic behavior of lithium ions in Li4Ti5O12 thin film electrodes is also conducted using cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT), and electrochemical impedance spectroscopy (EIS). Li4Ti5O12 thin film electrodes show favorable specific capacities and cycle performance. The chemical diffusion coefficients are found to be in a range of 10-15 to 10-12 cm2 s-1 determined by GITT method. The kinetic parameters obtained from impedance spectra as a function of the cell voltage are investigated in details. The decrease of the charge-transfer resistance (Rct) can be explained by the two-phase transition during lithium insertion into Li4Ti5O12.

  19. In-Situ Surface EXAFS at Chemically Modified Electrodes.

    DTIC Science & Technology

    1987-07-28

    characterization of underpotentially deposited copper on gold(ll) electrodes. [12] We now present an in-situ surface EXAFS study of electropolymerized... deposition or adsorption of metallic adlayers (6] or transition metal complexes. [7] In addition the electrode can act as a simple electron shuttle to...structure at all stages of polymer deposition . These values correlate very well with the known coordination member of six and a Ru-N distance of 2.056 A

  20. Integrated fast assembly of free-standing lithium titanate/carbon nanotube/cellulose nanofiber hybrid network film as flexible paper-electrode for lithium-ion batteries.

    PubMed

    Cao, Shaomei; Feng, Xin; Song, Yuanyuan; Xue, Xin; Liu, Hongjiang; Miao, Miao; Fang, Jianhui; Shi, Liyi

    2015-05-27

    A free-standing lithium titanate (Li4Ti5O12)/carbon nanotube/cellulose nanofiber hybrid network film is successfully assembled by using a pressure-controlled aqueous extrusion process, which is highly efficient and easily to scale up from the perspective of disposable and recyclable device production. This hybrid network film used as a lithium-ion battery (LIB) electrode has a dual-layer structure consisting of Li4Ti5O12/carbon nanotube/cellulose nanofiber composites (hereinafter referred to as LTO/CNT/CNF), and carbon nanotube/cellulose nanofiber composites (hereinafter referred to as CNT/CNF). In the heterogeneous fibrous network of the hybrid film, CNF serves simultaneously as building skeleton and a biosourced binder, which substitutes traditional toxic solvents and synthetic polymer binders. Of importance here is that the CNT/CNF layer is used as a lightweight current collector to replace traditional heavy metal foils, which therefore reduces the total mass of the electrode while keeping the same areal loading of active materials. The free-standing network film with high flexibility is easy to handle, and has extremely good conductivity, up to 15.0 S cm(-1). The flexible paper-electrode for LIBs shows very good high rate cycling performance, and the specific charge/discharge capacity values are up to 142 mAh g(-1) even at a current rate of 10 C. On the basis of the mild condition and fast assembly process, a CNF template fulfills multiple functions in the fabrication of paper-electrode for LIBs, which would offer an ever increasing potential for high energy density, low cost, and environmentally friendly flexible electronics.

  1. 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.

  2. 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.

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

    DOE PAGES

    He, Kai; Xin, Huolin L.; Zhao, Kejie; ...

    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

  4. 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.

  5. Carbon-Coated Silicon Nanowires on Carbon Fabric as Self-Supported Electrodes for Flexible Lithium-Ion Batteries.

    PubMed

    Wang, Xiaolei; Li, Ge; Seo, Min Ho; Lui, Gregory; Hassan, Fathy M; Feng, Kun; Xiao, Xingcheng; Chen, Zhongwei

    2017-03-22

    A novel self-supported electrode with long cycling life and high mass loading was developed based on carbon-coated Si nanowires grown in situ on highly conductive and flexible carbon fabric substrates through a nickel-catalyzed one-pot atmospheric pressure chemical vapor deposition. The high-quality carbon coated Si nanowires resulted in high reversible specific capacity (∼3500 mA h g(-1) at 100 mA g(-1)), while the three-dimensional electrode's unique architecture leads to a significantly improved robustness and a high degree of electrode stability. An exceptionally long cyclability with a capacity retention of ∼66% over 500 cycles at 1.0 A g(-1) was achieved. The controllable high mass loading enables an electrode with extremely high areal capacity of ∼5.0 mA h cm(-2). Such a scalable electrode fabrication technology and the high-performance electrodes hold great promise in future practical applications in high energy density lithium-ion batteries.

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

    SciTech Connect

    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

    2016-04-05

    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. 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.

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

    DOE PAGES

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

    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

  8. 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

  9. 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.

  10. Wetting Properties of Liquid Lithium on Stainless Steel and Enhanced Stainless Steel Surfaces

    NASA Astrophysics Data System (ADS)

    Fiflis, P.; Xu, W.; Raman, P.; Andruczyk, D.; Ruzic, D. N.; Curreli, D.

    2012-10-01

    Research into lithium as a first wall material has proven its ability to effectively getter impurities and reduce recycling of hydrogen ions at the wall. Current schemes for introducing lithium into a fusion device consist of lithium evaporators, however, as these devices evolve from pulsed to steady state, new methods will need to be employed such as the LIMIT concept of UIUC, or thin flowing film lithium walls. Critical to their implementation is understanding the interactions of liquid lithium with various surfaces. One such interaction is the wetting of materials by lithium, which may be characterized by the contact angle between the lithium and the surface. Experiments have been performed at UIUC into the contact angle of liquid lithium with a given surface, as well as methods to increase it. To reduce the oxidation rate of the droplets, the experiments were performed in vacuum, using a lithium injector to deposit drops on each surface. Among the materials investigated are stainless steel, both untreated and coated with a diamond like carbon (DLC) layer, molybdenum, and boronized molybdenum. The contact angle and its dependence on temperature is measured.

  11. Silicon surface-electrode ion traps for quantum information processing

    NASA Astrophysics Data System (ADS)

    Doret, S. Charles; Slusher, Richart

    2010-03-01

    The Georgia Tech Research Institute (GTRI) is designing, building, and testing scalable surface-electrode ion traps for quantum information applications, fabricated using silicon VLSI technology. A wide range of trap architectures have been developed, including a linear trap capable of holding long chains of equally spaced ions, a 90-degree X-junction, and an integrated micromirror with collection efficiency approaching 20%. Fabrication features that can be integrated with the surface electrodes include multilayer interconnects, optics for enhanced light collection, flexible optical access through beveled slots extending through the substrate, and recessed wire bonds for clear laser access across the trap surface. Traps are designed at GTRI using in-house codes that calculate trap fields, compute the full motion of ions confined in the trap, including micromotion, and optimize electrode shapes and transport waveforms using genetic algorithms. We will present designs and initial test results for several of these traps, as well as plans for their use in future experiments.

  12. Solid solution lithium alloy cermet anodes

    SciTech Connect

    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.

  13. The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface

    SciTech Connect

    Das, Atanu K.; Engelhard, Mark H.; Liu, Fei; Bullock, R. Morris; Roberts, John A.

    2013-12-02

    Glassy carbon electrodes have been activated for modification with azide groups and subsequent coupling with ferrocenyl reagents by a catalyst-free route using lithium acetylide-ethylenediamine complex, and also by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) route, both affording high surface coverages. Electrodes were preconditioned at ambient temperature under nitrogen, and ferrocenyl surface coverages obtained by CuAAC were comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen. The reaction of lithium acetylide-ethylenediamine with the azide-terminated electrode affords a 1,2,3-triazolyllithium-terminated surface that is active toward covalent C-C coupling reactions including displacement at an aliphatic halide and nucleophilic addition at an aldehyde. For example, surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry shows narrow, symmetric peaks indicating uniform attachment. Coverages are competitive with those obtained by the CuAAC route. X-ray photoelectron spectroscopic data, presented for each synthetic step, are consistent with the proposed reactions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  14. Surface analysis of new chlorpromazinium plastic membrane electrodes.

    PubMed

    Al-Shatti, L A; Marafie, H M; Shoukry, A F

    2008-01-22

    New chlorpromazinium (Cp) plastic membrane electrodes of the conventional type were constructed and characterized. They are based on incorporation of Cp-reineckate (CpRn) ion pair, Cp-phosphotungstate (Cp3PT), or Cp-phosphomolybdate (Cp3PM) ion associate into poly(vinyl chloride) membrane. The electrodes exhibited calibration graph slopes of 49.83, 52.87, and 61.30 mV/Cp concentration decade over life spans of 1, 5, and 3 days, respectively. All electrodes proved to be selective for Cp and have been applied to the assay of a pharmaceutical preparation. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), as well as scanning electron microscopy (SEM) showed that the limitation of the lifetime of the electrodes is attributed to leaching of the ion exchanger from the membrane into the test solution in addition to deformation of the surface.

  15. Modified carbon surfaces as "organic electrodes" that exhibit conductance switching.

    PubMed

    Solak, Ali Osman; Eichorst, Laura R; Clark, William J; McCreery, Richard L

    2003-01-15

    Glassy carbon (GC) surfaces modified with monolayers of biphenyl and nitrobiphenyl molecules were examined as voltammetric electrodes for ferrocene, benzoquinone, and tetracyanoquinodimethane electrochemistry in acetonitrile. The modified electrodes exhibited slower electron transfer than unmodified GC, by factors that varied with the monolayer and redox system. However, after a negative potential excursion to approximately -2.0 V versus Ag+/Ag, the modified electrodes exhibited much faster electron-transfer kinetics, approaching those observed on unmodified GC. The effect is attributed to an apparently irreversible structural change in the biphenyl or nitrobiphenyl monolayer, which increases the rate of electron tunneling. The transition to the "ON" state is associated with electron injection into the monolayer similar to that observed in previous spectroscopic investigations and causes a significant decrease in the calculated HOMO-LUMO gap for the monolayer molecule. Once the monolayer is switched ON, it supports rapid electron exchange with outer-sphere redox systems, but not with dopamine, which requires adsorption to the GC surface. The increase in electron-transfer rate with electron injection is consistent with an increase in electron tunneling rate through the monolayer, caused by a significant decrease in tunneling barrier height. The ON electrode can reduce biphenyl- or nitrobiphenyldiazonium reagent in solution to permit formation of a second modification layer of biphenyl or nitrobiphenyl molecules. This "double derivatization" procedure was used to prepare tetraphenyl- and nitrotetraphenyl-modified electrodes, which exhibit significantly slower electron transfer than their biphenyl and nitrobiphenyl counterparts. A "switching" electrode may have useful properties for electroanalytical applications and possibly in electrocatalysis. In addition, the ON state represents an "organic electrode" in which electron transfer occurs at an interface between an

  16. Characteristics of coke carbon modified with mesophase-pitch as a negative electrode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sato, Yuichi; Kikuchi, Yasuo; Nakano, Takeshi; Okuno, Gaku; Kobayakawa, Koichi; Kawai, Takanobu; Yokoyama, Akira

    To increase the charge-discharge capacity of carbon electrodes for lithium ion secondary batteries, coke carbon, a relatively cheap material, was modified with mesophase-pitch carbon by a heat treatment. While coke carbon powder, mesophase-pitch, and a mixture thereof (4:1 by weight) supplied between 0 and 1.5 V vs. Li/Li + an initial discharge capacity of about 295 mAh/g, 310 mAh/g, and 310 mAh/g, respectively, the modified coke deintercalated 400 mA h/g of lithium with a high degree of reversibility. The difference in capacity between the modified carbon and mixture are discussed based on the shape of their current-potential curves and their galvanostatic charge-discharge curves.

  17. Application of surface enhanced Raman spectroscopy to the study of SOFC electrode surfaces.

    PubMed

    Li, Xiaxi; Blinn, Kevin; Fang, Yingcui; Liu, Mingfei; Mahmoud, Mahmoud A; Cheng, Shuang; Bottomley, Lawrence A; El-Sayed, Mostafa; Liu, Meilin

    2012-05-07

    SERS provided by sputtered silver was employed to detect trace amounts of chemical species on SOFC electrodes. Considerable enhancement of Raman signal and lowered detection threshold were shown for coked nickel surfaces, CeO(2) coatings, and cathode materials (LSM and LSCF), suggesting a viable approach to probing electrode degradation and surface catalytic mechanism.

  18. High performance screen-printed electrodes prepared by a green solvent approach for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Gören, A.; Mendes, J.; Rodrigues, H. M.; Sousa, R. E.; Oliveira, J.; Hilliou, L.; Costa, C. M.; Silva, M. M.; Lanceros-Méndez, S.

    2016-12-01

    New inks based on lithium iron phosphate and graphite for cathode and anode, respectively, were developed for printable lithium-ion batteries using the "green solvent" N,N‧-dimethylpropyleneurea (DMPU) and poly(vinylidene fluoride), PVDF, as a binder. The results were compared with the ones from inks developed with the conventionally used solvent N-methyl-2-pyrrolidone, NMP. The rheological properties of the PVDF/DMPU binder solution shows a more pronounced shear thinning behavior than the PVDF/NMP solution. Cathode inks prepared with 2.25 mL and 2.50 mL of DMPU for 1 g of electrode mass show an apparent viscosity of 3 Pa s and 2 Pa s for a shear rate of 100 s-1, respectively, being therefore processable by screen-printing or doctor blade techniques. The electrodes prepared with DMPU and processed by screen-printing show a capacity of 52 mAh g-1 at 2C for the cathode and 349 mAh g-1 at C/5 for the anode, after 45 charge-discharge cycles. The electrochemical performance of both electrodes was evaluated in a full-cell and after 9 cycles, the discharge capacity value is 81 mAh g-1, showing a discharge capacity retention of 64%. The new inks presented in this work are thus suitable for the development of printed batteries and represent a step forward towards more environmental friendly processes.

  19. 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.

  20. Mass spectrometry investigations on electrolyte degradation products for the development of nanocomposite electrodes in lithium ion batteries.

    PubMed

    Gireaud, Laurent; Grugeon, Sylvie; Pilard, Serge; Guenot, Pierre; Tarascon, Jean-Marie; Laruelle, Stephane

    2006-06-01

    In the continuing challenge to find new routes to improve the performance of commercial lithium ion batteries cycling in alkyl carbonate-based electrolyte solutions, original designs, and new electrode materials are under active worldwide investigation. Our group has focused on the electrochemical behavior of a new generation of nanocomposite electrodes showing improved capacities (up to 3 times the capacity of conventional electrode materials). However, moving down to "nanometric-scale" active materials leads to a significant increase in electrolyte degradation, compared to that taking place within commercial batteries. Postmortem electrolyte studies on experimental coin cells were conducted to understand the degradation mechanisms. Structural analysis of the organic degradation products were investigated using a combination of complementary high-resolution mass spectrometry techniques: desorption under electron impact, electrospray ionization, and gas chromatography coupled to a mass spectrometer equipped with electron impact and chemical ionization ion sources. Numerous organic degradation products such as ethylene oxide oligomers (with methyl, hydroxyl, phosphate, and methyl carbonate endings) have been characterized. In light of our findings, possible chemical or electrochemical pathways are proposed to account for their formation. A thorough knowledge of these degradation mechanisms will enable us to propose new electrolyte formulations to optimize nanocomposite-based lithium ion battery performance.

  1. Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

    DOE PAGES

    Sougrati, Moulay T.; Darwiche, Ali; Liu, Xiaohiu; ...

    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

  2. Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

    SciTech Connect

    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 require 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.

  3. Microstructure formation of lithium-ion battery electrodes during drying - An ex-situ study using cryogenic broad ion beam slope-cutting and scanning electron microscopy (Cryo-BIB-SEM)

    NASA Astrophysics Data System (ADS)

    Jaiser, Stefan; Kumberg, Jana; Klaver, Jop; Urai, Janos L.; Schabel, Wilhelm; Schmatz, Joyce; Scharfer, Philip

    2017-03-01

    Properties of lithium-ion battery electrodes relate to the complex microstructure that develops during solvent removal. We use cryogenic scanning electron microscopy in combination with broad ion beam slope-cutting (Cryo-BIB-SEM) for the ex-situ imaging of film formation in battery electrodes. Drying of anode films is quenched by cryo-preservation in slushy nitrogen at systematically increasing drying times, followed by SEM imaging under cryogenic conditions. Energy dispersive x-ray spectroscopy (EDS) and image processing of segmented cross-sections are used to analyze the development of component gradients with time. We find electrode films to shrink homogeneously and not in a top-down consolidation process as previously hypothesized. Binder gradients evolve in the liquid phase and initiate solvent diffusion from the bulk to the surface, thereby dragging binder towards the surface. Capillary transport is identified as a fundamental process that directly impacts drying kinetics and binder distribution.

  4. Lithium-based surfaces controlling fusion plasma behavior at the plasma-material interfacea)

    NASA Astrophysics Data System (ADS)

    Allain, Jean Paul; Taylor, Chase N.

    2012-05-01

    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.

  5. Heating rate and electrode charging measurements in a scalable, microfabricated, surface-electrode ion trap

    NASA Astrophysics Data System (ADS)

    Allcock, D. T. C.; Harty, T. P.; Janacek, H. A.; Linke, N. M.; Ballance, C. J.; Steane, A. M.; Lucas, D. M.; Jarecki, R. L.; Habermehl, S. D.; Blain, M. G.; Stick, D.; Moehring, D. L.

    2012-06-01

    We characterise the performance of a surface-electrode ion "chip" trap fabricated using established semiconductor integrated circuit and micro-electro-mechanical-system (MEMS) microfabrication processes, which are in principle scalable to much larger ion trap arrays, as proposed for implementing ion trap quantum information processing. We measure rf ion micromotion parallel and perpendicular to the plane of the trap electrodes, and find that on-package capacitors reduce this to ≲10 nm in amplitude. We also measure ion trapping lifetime, charging effects due to laser light incident on the trap electrodes, and the heating rate for a single trapped ion. The performance of this trap is found to be comparable with others of the same size scale.

  6. The surface core level shift for lithium at the surface of lithium borate

    NASA Astrophysics Data System (ADS)

    Wooten, David; Ketsman, I.; Xiao, Jie; Losovyj, Ya. B.; Petrosky, J.; McClory, J.; Burak, Ya. V.; Adamiv, V. T.; Dowben, P. A.

    2010-01-01

    The shallow Li 1s core level exhibits a surface-to-bulk core level shift for the stoichiometric Li 2B 4O 7(1 1 0) surface. Angle-resolved photoemission spectroscopy was used to indentify Li 1s bulk and surface core level components at binding energies -56.5±0.4 and -53.7±0.5 eV, respectively. We find photoemission evidence for surface states of Li 2B 4O 7(1 1 0) that exist in the gap of the projected bulk density of states. The existence of surface states is consistent with the large surface-to-bulk core level shift for the Li 1s core.

  7. 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.

  8. New tetradecyltrimethylammonium-selective electrodes: surface composition and topography as correlated with electrode's life span.

    PubMed

    Marafie, Hayat M; Al-Shammari, Tahani F; Shoukry, Adel F

    2012-03-15

    Two conventional plastic membrane electrodes that are selective for the tetradecyltrimethylammonium cation (TTA) have been prepared. The ion exchangers of these sensors were the ion associate, TTA-PT, and the ion aggregate, TTA-PSS, where PT and PSS are phosphotungstate and polystyrene sulfonate, respectively. The following performance characteristics of the TTA-PT- and TTA-PSS-containing electrodes were found: conditioning time of 30 and 20 min; potential response of 58.2 and 61.1 mV/TTA concentration decade; rectilinear concentration ranges of 2.0 × 10(-5)-5.0 × 10(-2) and 1.5 × 10(-5)-7.9 × 10(-2) mol L(-1); average working pH ranges of 4.0-10.5 and 3.8-10.7; life spans of 20 and 28 weeks, and isothermal temperature coefficients of 4.44 × 10(-4) and 6.10 × 10(-4)V/°C, respectively. Both electrodes exhibited high selectivity for TTA with an increasing number of inorganic and quaternary ammonium surfactant cations. These electrodes have been successfully applied to assay an antiseptic formulation containing TTA. Surface analyses using electron microscopy and X-ray photoelectron spectroscopy were used to determine the cause of the limited life span of plastic membrane electrodes.

  9. 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

  10. 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.

  11. Approaching the downsizing limit of silicon for surface-controlled lithium storage.

    PubMed

    Wang, Bin; Li, Xianglong; Luo, Bin; Hao, Long; Zhou, Min; Zhang, Xinghao; Fan, Zhuangjun; Zhi, Linjie

    2015-03-04

    Graphene-sheet-supported uniform ultrasmall (≈3 nm) silicon quantum dots have been successfully synthesized by a simple and effective self-assembly strategy, exhibiting unprecedented fast, surface-controlled lithium-storage behavior and outstanding lithium-storage properties including extraordinary rate capability and remarkable cycling stability, attributable to the intrinsic role of approaching the downsizing limit of silicon.

  12. Compatibility of lithium plasma-facing surfaces with high edge temperatures in the Lithium Tokamak Experiment (LTX)

    NASA Astrophysics Data System (ADS)

    Majeski, Dick

    2016-10-01

    High edge electron temperatures (200 eV or greater) have been measured at the wall-limited plasma boundary in the Lithium Tokamak eXperiment (LTX). High edge temperatures, with flat electron temperature profiles, are a long-predicted consequence of low recycling boundary conditions. The temperature profile in LTX, measured by Thomson scattering, varies by as little as 10% from the plasma axis to the boundary, determined by the lithium-coated high field-side wall. The hydrogen plasma density in the outer scrape-off layer is very low, 2-3 x 1017 m-3 , consistent with a low recycling metallic lithium boundary. The plasma surface interaction in LTX is characterized by a low flux of high energy protons to the lithium PFC, with an estimated Debye sheath potential approaching 1 kV. Plasma-material interactions in LTX are consequently in a novel regime, where the impacting proton energy exceeds the peak in the sputtering yield for the lithium wall. In this regime, further increases in the edge temperature will decrease, rather than increase, the sputtering yield. Despite the high edge temperature, the core impurity content is low. Zeff is 1.2 - 1.5, with a very modest contribution (<0.1) from lithium. So far experiments are transient. Gas puffing is used to increase the plasma density. After gas injection stops, the discharge density is allowed to drop, and the edge is pumped by the low recycling lithium wall. An upgrade to LTX which includes a 35A, 20 kV neutral beam injector to provide core fueling to maintain constant density, as well as auxiliary heating, is underway. Two beam systems have been loaned to LTX by Tri Alpha Energy. Additional results from LTX, as well as progress on the upgrade - LTX- β - will be discussed. Work supported by US DOE contracts DE-AC02-09CH11466 and DE-AC05-00OR22725.

  13. 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.

  14. 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.

  15. Probing and mapping electrode surfaces in solid oxide fuel cells.

    PubMed

    Blinn, Kevin S; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A; Liu, Meilin

    2012-09-20

    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 conversion(2). 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 degradation(8-12). 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 deposition(8, 10, 13, 14) ("coking") and sulfur poisoning(11, 15) and the manner in which surface modifications stave off this degradation(16). 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

  16. 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.

  17. 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.

  18. 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

  19. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries.

    PubMed

    Roberts, Matthew R; Madsen, Alex; Nicklin, Chris; Rawle, Jonathan; Palmer, Michael G; Owen, John R; Hector, Andrew L

    2014-04-03

    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.

  20. LiNi 0.8 Co 0.2 O 2 -based high power lithium-ion battery positive electrodes analyzed by x-ray photoelectron spectroscopy: 1. Fresh electrode

    SciTech Connect

    Haasch, Richard T.; Abraham, Daniel A.

    2016-12-01

    High-power lithium-ion batteries are rapidly replacing the nickel metal hydride batteries currently used for energy storage in hybrid electric vehicles. Widespread commercialization of these batteries for vehicular applications is, however, limited by calendar-life performance, thermal abuse characteristics, and cost. The Advanced Technology Development Program was established by the U.S. Department of Energy to address these limitations. An important objective of this program was the development and application of diagnostic tools that provide unique ways to investigate the phenomena that limit lithium-ion cell life, performance, and safety characteristics. This report introduces a set of six Surface Science Spectra xray photoelectron spectroscopy (XPS) comparison records of data collected from positive electrodes (cathode) harvested from cylindrically wound, 18650-type, 1 A h capacity cells. The cathodes included in this study are (1) fresh, (2) following three formation cycles, (3) following calendar-life test for 12 weeks at 40 C, 60% state-of-charge (SOC), (4) following calendar-life test for 8 weeks at 50 C, 60% SOC, (5) following calendar-life test for 8 weeks at 60 C, 60% SOC, and (6) following calendar-life test for 2 weeks at 70 C, 60% SOC.

  1. 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.

  2. 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).

  3. 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.

  4. Thin film rechargeable electrodes based on conductive blends of nanostructured olivine LiFePO4 and sucrose derived nanocarbons for lithium ion batteries.

    PubMed

    Praveen, P; Jyothsna, U; Nair, Priya; Ravi, Soumya; Balakrishnan, A; Subramanian, K R V; Nair, A Sreekumaran; Nair, V Shantikumar; Sivakumar, N

    2013-08-01

    The present study provides the first reports of a novel approach of electrophoretic co-deposition technique by which titanium foils are coated with LiFePO4-carbon nanocomposites synthesized by sol gel route and processed into high-surface area cathodes for lithium ion batteries. The study elucidates how sucrose additions as carbon source can affect the surface morphology and the redox reaction behaviors underlying these cathodes and thereby enhance the battery performance. The phase and morphological analysis were done using XRD and XPS where the LiFePO4 formed was confirmed to be a high purity orthorhombic system. From the analysis of the relevant electrochemical parameters using cyclic voltammetry and electrochemical impedance spectroscopy, a 20% increment and 90% decrement in capacity and impedance values were observed respectively. The composite electrodes also exhibited a specific capacity of 130 mA h/g. It has been shown that cathodes based on such composite systems can allow significant room for improvement in the cycling performance at the electrode/electrolyte interface.

  5. The electrode as organolithium reagent: catalyst-free covalent attachment of electrochemically active species to an azide-terminated glassy carbon electrode surface.

    PubMed

    Das, Atanu K; Engelhard, Mark H; Liu, Fei; Bullock, R Morris; Roberts, John A S

    2013-12-02

    The reaction of a lithium acetylide-ethylenediamine complex with azide-terminated glassy carbon surfaces affords 1,2,3-triazolyllithium surface groups that are active toward covalent C-C coupling reactions, including salt metathesis with an aliphatic halide and nucleophilic addition at an aldehyde. Surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry of electrode samples shows narrow, symmetric peaks indicating uniform attachment. X-ray photoelectron and reflectance infrared spectroscopic data provide further support for the surface-attached products. Formation of the 1,2,3-triazolyllithium linkage requires neither a catalyst nor a strained alkyne. Coverages obtained by this route are similar to those obtained by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) of ethynylferrocene with surface azides. Preconditioning of the glassy carbon disk electrodes at ambient temperature under nitrogen affords coverages comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen.

  6. Electrocatalysis of lithium polysulfides: current collectors as electrodes in Li/S battery configuration.

    PubMed

    Babu, Ganguli; Ababtain, Khalid; Ng, K Y Simon; Arava, Leela Mohana Reddy

    2015-03-05

    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.

  7. 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

  8. Hot-rolling nanowire transparent electrodes for surface roughness minimization.

    PubMed

    Hosseinzadeh Khaligh, Hadi; Goldthorpe, Irene A

    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.

  9. Long-range surface plasmons in electrode structures

    NASA Technical Reports Server (NTRS)

    Stegeman, G. I.; Burke, J. J.

    1983-01-01

    Surface polaritons guided by symmetric double metal film structures are analyzed, with particular attention given to the attenuation of the two long-range modes that occur. It is found that long-range surface plasmon polariton modes do exist for double electrode structures over a limited range of material parameters. Guided by thin metal electrodes, surface plasmon polaritons can achieve millimeter plus propagation distances in the near infrared. It is pointed out that if the slab is electrooptic, then very low voltages will be needed to manipulate the waves. The fact that long-range modes exist simultaneously with junction tunnel plasmons may be of use in providing directional radiation from light-emitting junctions or the inverse process of light to electrical energy conversion.

  10. 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

  11. 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.

  12. 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.

  13. Complementary X-ray and neutron radiography study of the initial lithiation process in lithium-ion batteries containing silicon electrodes

    NASA Astrophysics Data System (ADS)

    Sun, Fu; Markötter, Henning; Manke, Ingo; Hilger, André; Alrwashdeh, Saad S.; Kardjilov, Nikolay; Banhart, John

    2017-03-01

    Complementary in operando X-ray radiography and neutron radiography measurements were conducted to investigate and visualize the initial lithiation in silicon-electrode lithium-ion batteries. By means of X-ray radiography, a significant volume expansion of Si particles and the Si electrode during the first discharge was observed. In addition, many Si particles were found that never undergo electrochemical reactions. These findings were confirmed by neutron radiography, which, for the first time, showed the process of Li alloying with the Si electrode during initial lithiation. These results demonstrate that complementary X-ray and neutron radiography is a powerful tool to investigate the lithiation mechanisms inside Si-electrode based lithium-ion batteries.

  14. 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.

  15. 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.

  16. 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

  17. Synthese, etude structurale et electrochimique des materiaux d'electrode positive d'oxydes mixtes lithium cobalt nickel oxide (0 /= 1) pour les batteries rechargeables au lithium

    NASA Astrophysics Data System (ADS)

    Grincourt, Yves

    Depuis une dizaine d'annees, on observe un interet grandissant pour les batteries rechargeables au lithium de tension superieure a 4 volts. La commercialisation de ces batteries pour l'electronique grand marche tend de plus en plus a supplanter celle des accumulateurs Ni-Cd et Ni-MH, de tension nominate 1,2 V. Ces batteries au lithium font appel a des materiaux d'electrode positive (cathode a la decharge) du type oxydes mixtes de metaux de transition LiMnO 2, LiMn2O4, LiNiO2 ou LiCoO2. Si le compose LiCoO2 est relativement aise a synthetiser, il n'en demeure pas moins que le cobalt reste un metal plus couteux compare au nickel et au manganese. La synthese de LiNiO2, quart a elle, demeure un probleme du point de vue stoechiometrique. Un defaut de lithium (5 a 10% molaire) conduira a des proprietes electrochimiques mediocres de la batterie. Dans cette etude nous nous proposons donc de preparer par voie humide et par voie seche les materiaux d'electrode positive de la famille LiCoyNi1-yO2 aver (0 ≤ y ≤ 1) et d'etudier en detail l'influence du pourcentage de nickel et de cobalt sur les proprietes electrochimiques des oxydes mixtes Li-Ni-Co. Une des caracteristiques est la morphologie plus fine des poudres de materiaux, observes par microscopie electronique a balayage (MEB). Un traitement thermique a plus basse temperature (750°C) que pour LiCoO2 (850°C) ainsi qu'un leger exces de lithium dans la preparation, ont permis d'aboutir a un materiau de stoechiometrie quasi parfaite. Neanmoins, le role de pilfer joue par 2 a 4% de moles de Ni2+ presents sur les sites lithium, permet de conserver intacte la structure hexagonale de la maille entre deux cycles consecutifs. Afin de mieux comprendre l'influence du vieillissement dune demi-pile Li/LiMeO2 (Me = Ni, Co) a temperature ambiante, des etudes electrochimiques et d'impedance spectroscopique ont ete menees en parallele. Le vieillissement de la cellule s'accompagne seulement dune chute de son potentiel due a son auto

  18. 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.

  19. Surface oxidized mesoporous carbons derived from porous silicon as dual polysulfide confinement and anchoring cathodes in lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Carter, Rachel; Ejorh, Dennis; Share, Keith; Cohn, Adam P.; Douglas, Anna; Muralidharan, Nitin; Tovar, Trenton M.; Pint, Cary L.

    2016-10-01

    Despite widespread focus on porous carbons for lithium-sulfur battery cathode materials, electrode design to preserve mass-specific performance and sustained extended cycling stability remains a challenge. Here, we demonstrate electrochemically etched porous silicon as a sacrificial template to produce a new class of functional mesoporous carbons optimized for dual chemical and physical confinement of soluble polysulfides in lithium-sulfur battery cathodes. Melt infiltration loading of sulfur at 60 wt% enables initial discharge capacity of 1350 mAh/gsulfur at rates of 0.1 C - approaching theoretical capacity of 1675 mAh/gsulfur. Cycling performance measured at 0.2 C indicates 81% capacity retention measured over 100 cycles with 830 mAh/gsulfur capacity. Unlike other carbons, this template combines structural properties necessary for sulfur containment and polysulfide confinement to achieve high specific capacity, but also boasts surface-bound oxygen-containing functional groups that are able to chemically anchor the soluble Li2Sn species on the interior of the mesoporous carbon to sustain cycling performance. In turn, this elucidates a scalable and competitive material framework that is capable, without the addition of additional membranes or inactive anchoring materials, of providing the simultaneous anchoring and confinement effects necessary to overcome performance limitations in lithium sulfur batteries.

  20. Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes

    SciTech Connect

    Gilbert, James A.; Bareno, Javier; Spila, Timothy; Trask, Stephen E.; Miller, Dean J.; Polzin, Bryant J.; Jansen, Andrew N.; Abraham, Daniel P.

    2016-09-22

    Energy density of full cells containing layered-oxide positive electrodes can be increased by raising the upper cutoff voltage above the current 4.2 V limit. In this article we examine aging behavior of cells, containing LiNi0.5Co0.2Mn0.3O2 (NCM523)-based positive and graphite-based negative electrodes, which underwent up to ~400 cycles in the 3-4.4 V range. Electrochemistry results from electrodes harvested from the cycled cells were obtained to identify causes of cell performance loss; these results were complemented with data from X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) measurements. Our experiments indicate that the full cell capacity fade increases linearly with cycle number and results from irreversible lithium loss in the negative electrode solid electrolyte interphase (SEI) layer. The accompanying electrode potential shift reduces utilization of active material in both electrodes and causes the positive electrode to cycle at higher states-of-charge. Here, full cell impedance rise on aging arises primarily at the positive electrode and results mainly from changes at the electrode-electrolyte interface; the small growth in negative electrode impedance reflects changes in the SEI layer. Our results indicate that cell performance loss could be mitigated by modifying the electrode-electrolyte interfaces through use of appropriate electrode coatings and/or electrolyte additives.

  1. Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes

    DOE PAGES

    Gilbert, James A.; Bareno, Javier; Spila, Timothy; ...

    2016-09-22

    Energy density of full cells containing layered-oxide positive electrodes can be increased by raising the upper cutoff voltage above the current 4.2 V limit. In this article we examine aging behavior of cells, containing LiNi0.5Co0.2Mn0.3O2 (NCM523)-based positive and graphite-based negative electrodes, which underwent up to ~400 cycles in the 3-4.4 V range. Electrochemistry results from electrodes harvested from the cycled cells were obtained to identify causes of cell performance loss; these results were complemented with data from X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) measurements. Our experiments indicate that the full cell capacity fade increases linearly withmore » cycle number and results from irreversible lithium loss in the negative electrode solid electrolyte interphase (SEI) layer. The accompanying electrode potential shift reduces utilization of active material in both electrodes and causes the positive electrode to cycle at higher states-of-charge. Here, full cell impedance rise on aging arises primarily at the positive electrode and results mainly from changes at the electrode-electrolyte interface; the small growth in negative electrode impedance reflects changes in the SEI layer. Our results indicate that cell performance loss could be mitigated by modifying the electrode-electrolyte interfaces through use of appropriate electrode coatings and/or electrolyte additives.« less

  2. Polyvinyl Alcohol-derived carbon nanofibers/carbon nanotubes/sulfur electrode with honeycomb-like hierarchical porous structure for the stable-capacity lithium/sulfur batteries

    NASA Astrophysics Data System (ADS)

    Deng, Nanping; Kang, Weimin; Ju, Jingge; Fan, Lanlan; Zhuang, Xupin; Ma, Xiaomin; He, Hongsheng; Zhao, Yixia; Cheng, Bowen

    2017-04-01

    The honeycomb-like hierarchical porous carbon nanofibers (PCNFs)-carbon nanotubes (CNTs)-sulfur(S) composite electrode is successfully desgined and prepared through ball-milling and heating method, in which the PCNFs are carbonized from fibers in the membrane composed of Polyvinyl Alcohol and Polytetrafluoroethylene by electro-blown spinning technology. The prepared PCNFs-CNTs-S composite are regarded as cathode for lithium-sulfur battery. The tailored porous structure and CNTs in the composite facilitate construction of a high electrical conductive pathway and store more S/polysulfides, and the dissoluble loss of intermediate S species in electrolyte can also be restrained because of acidized PVA-based porous carbon nanofibers. Meanwhile, the porous strcucture and CNTs can effectively alleviate volume changes in battery cycling process. Moreover, the presence of LiNO3 in electrolyte helps the electrochemical oxidation of Li2S and LiNO3-derived surface film effectively suppresses the migration of soluble polysulfide to the Li anode surface. Therefore, the obtained PCNFs-CNTs-S cathode exhibits excellent performance in Li-S battery with a high initial discharge capacity as high as 1302.9 mAh g-1, and super stable capacity retention with 809.1 mAh g-1 after 300 cycles at the current density of 837.5 mA g-1 (0.5 C). And the rate capability of PCNFs-CNTs-S electrode is much better than those of CNTs-S and PCNFs-S electrodes.

  3. Liquid Lithium Limiter Effects on Tokamak Plasmas and Plasma-Liquid Surface Interactions

    SciTech Connect

    R. Kaita; R. Majeski; R. Doerner; G. Antar; M. Baldwin; R. Conn; P. Efthimion; M. Finkenthal; D. Hoffman; B. Jones; S. Krashenninikov; H. Kugel; S. Luckhardt; R. Maingi; J. Menard; T. Munsat; D. Stutman; G. Taylor; J. Timberlake; V. Soukhanovskii; D. Whyte; R. Woolley; L. Zakharov

    2002-10-15

    We present results from the first experiments with a large area liquid lithium limiter in a magnetic fusion device, and its effect on improving plasma performance by reducing particle recycling. Using large area liquid metal surfaces in any major fusion device is unlikely before a test on a smaller scale. This has motivated its demonstration in the CDX-U spherical torus with a unique, fully toroidal lithium limiter. The highest current discharges were obtained with a liquid lithium limiter. There was a reduction in recycling, as indicated by a significant decrease in the deuterium-alpha emission and oxygen radiation. How these results might extrapolate to reactors is suggested in recycling/retention experiments with liquid lithium surfaces under high-flux deuterium and helium plasma bombardment in PISCES-B. Data on deuterium atoms retained in liquid lithium indicate retention of all incident ions until full volumetric conversion to lithium deuteride. The PISCES-B results also show a material loss mechanism that lowers the maximum operating temperature compared to that for the liquid surface equilibrium vapor pressure. This may restrict the lithium temperature in reactors.

  4. 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.

  5. Compositional analysis of passivating surface film formed on carbon electrode in organic electrolytic solution using in-situ spectroelectrochemical technique

    NASA Astrophysics Data System (ADS)

    Pyun, Su-Il

    1999-02-01

    In-situ spectroelectrochemical technique has been applied to investigate passivating surface film on porous carbon electrode and plasma enhanced chemical vapour deposited (PECVD) carbon film electrode in organic electrolytic solution consisting of ethylene carbonate (EC) and diethyl carbonate (DEC) solvent, and 1 M LiPF6 and LiAsF6. Water impurity with the concentration of 0 M, 0.02 M, 0.05 M, and 0.1 M H20 was added to 1 M LiPF6-EC/DEC solution. In-situ Fourier transform infra-red (FTIR) spectra of the surface film on both electrodes with the constituents of ROCO2Li, Li2CO3, and LixPFy suggested that the reduction of EC to ROCO2Li runs via a one-electron transfer pathway as a result of diffusion of water through the surface film, and then Li2CO3 formation proceeds simultaneously by the chemical reaction of ROCO2Li with water. From the measured potential dependence of the amount of the salt reduction products, it is suggested that the surface film formed in 1 M LiPF6EC/DEC solution gives a poorer passivity as compared with that formed in 1 M LiAsF6-EC/DEC solution, which is due to the considerable interference of LiPE6 salt reduction with the compact sedimentation of ROCO2Li on the electrode. In-situ FFIR spectra of the surface film showed that all the peak intensities of the three constituents significantly increase with increasing water content under application of the negative potentials with respect to open circuit potential (OCP). From these experimental results, the dependence of the passivity of the surface film on the carbon electrode on the water concentration of the electrolyte, as well as on the lithium salt type, was discussed in view of the salt and solvent reactivities.

  6. 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.

  7. 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.

  8. Nanoscale Decoration of Electrode Surfaces with an STM

    DTIC Science & Technology

    1999-05-30

    covered Au( 111) surface due to underpotential deposition . E,,,P, = + 10 mV vs. Cu/Cu++, E, = - 30 mV, I, = 2 nA. (b) Same area, but after anodic...Abstract The tip of a scanning tunnelling microscope (STM) has been used to deposit nanometer-sized clusters of copper or silver on bare and thiol...covered gold electrode surfaces at predetermined positions. First, metal is deposited electrochemically onto the STM tip, then the clusters are formed by a

  9. 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.

  10. 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.

  11. Spherical Torus Plasma Interactions with Large-area Liquid Lithium Surfaces in CDX-U

    SciTech Connect

    R. Kaita; R. Majeski; M. Boaz; P. Efthimion; B. Jones; D. Hoffman; H. Kugel; J. Menard; T. Munsat; A. Post-Zwicker; V. Soukhanovskii; J. Spaleta; G. Taylor; J. Timberlake; R. Woolley; L. Zakharov; M. Finkenthal; D. Stutman; G. Antar; R. Doerner; S. Luckhardt; R. Maingi; M. Maiorano; S. Smith

    2002-01-18

    The Current Drive Experiment-Upgrade (CDX-U) device at the Princeton Plasma Physics Laboratory (PPPL) is a spherical torus (ST) dedicated to the exploration of liquid lithium as a potential solution to reactor first-wall problems such as heat load and erosion, neutron damage and activation, and tritium inventory and breeding. Initial lithium limiter experiments were conducted with a toroidally-local liquid lithium rail limiter (L3) from the University of California at San Diego. Spectroscopic measurements showed a clear reduction of impurities in plasmas with the L3, compared to discharges with a boron carbide limiter. The evidence for a reduction in recycling was less apparent, however. This may be attributable to the relatively small area in contact with the plasma, and the presence of high-recycling surfaces elsewhere in the vacuum chamber. This conclusion was tested in subsequent experiments with a fully toroidal lithium limiter that was installed above the floor of the vacuum vessel. The new limiter covered over ten times the area of the L3 facing the plasma. Experiments with the toroidal lithium limiter have recently begun. This paper describes the conditioning required to prepare the lithium surface for plasma operations, and effect of the toroidal liquid lithium limiter on discharge performance.

  12. Lithium-ion capacitors using carbide-derived carbon as the positive electrode - A comparison of cells with graphite and Li4Ti5O12 as the negative electrode

    NASA Astrophysics Data System (ADS)

    Rauhala, Taina; Leis, Jaan; Kallio, Tanja; Vuorilehto, Kai

    2016-11-01

    The use of carbide-derived carbon (CDC) as the positive electrode material for lithium-ion capacitors (LICs) is investigated. CDC based LIC cells are studied utilizing two different negative electrode materials: graphite and lithium titanate Li4Ti5O12 (LTO). The graphite electrodes are prelithiated before assembling the LICs, and LTO containing cells are studied with and without prelithiation. The rate capability and cycle life stability during 1000 cycles are evaluated by galvanostatic cycling at current densities of 0.4-4 mA cm-2. The CDC shows a specific capacitance of 120 F g-1 in the organic lithium-containing electrolyte, and the LICs demonstrate a good stability over 1000 charge-discharge cycles. The choice of the negative electrode is found to have an effect on the utilization of the CDC positive electrode during cycling and on the specific energy of the device. The graphite/CDC cell delivers a maximum specific discharge energy of 90 Wh kg-1 based on the total mass of active material in the cell. Both the prelithiated and non-prelithiated LTO/CDC cells show a specific energy of around 30 Wh kg-1.

  13. Tunable Bloch surface waves in anisotropic photonic crystals based on lithium niobate thin films.

    PubMed

    Kovalevich, Tatiana; Ndao, Abdoulaye; Suarez, Miguel; Tumenas, Saulius; Balevicius, Zigmas; Ramanavicius, Arunas; Baleviciute, Ieva; Häyrinen, Markus; Roussey, Matthieu; Kuittinen, Markku; Grosjean, Thierry; Bernal, Maria-Pilar

    2016-12-01

    We present an original type of one-dimensional photonic crystal that includes one anisotropic layer made of a lithium niobate thin film. We demonstrate the versatility of such a device sustaining different Bloch surface waves (BSWs), depending on the orientation of the incident wave. By varying the orientation of the illumination of the multilayer, we measured an angle variation of 7° between the BSWs corresponding to the extraordinary and the ordinary index of the lithium niobate thin film. The potential of such a platform opens the way to novel tunable and active planar optics based on the electro- and thermo-optical properties of lithium niobate.

  14. 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..

  15. Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems

    SciTech Connect

    Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.; Deng, Daniel Z.; Yang, Jihui; Xiao, Jie

    2016-01-01

    In recent years room temperature Li+ ion conductors have been intensively revisited in order to develop safe lithium ion (Li-ion) batteries and beyond that can be deployed in the electrical vehicles. Through careful modification on materials synthesis, promising solid Li+ conductors with high ionic conductivity, competitve with liquid electrolytes, have been demonstrated. However, the integration of those highly conductive solid electrolytes into the whole system is still very challenging mainly due to the high impedance existing in the different interfaces throughout the entire battery structure. Herein , this review paper focuses on the overview of the interfacial behaviors between Li+ conductors and cathode/anode materials. The origin, evolution and potential solutions to reuce these interfacial impedances are reviewed for various battery systems spanning from Li-ion, lithium sulfur (Li-S), lithium oxygen (Li-O2) batteries to lithium metal protection. The predicted gravimetric and volumetric energy densities at different scenarios are also discussed along with the prospectives for further development of solid state batteries.

  16. Highly Oriented Graphene Sponge Electrode for Ultra High Energy Density Lithium Ion Hybrid Capacitors.

    PubMed

    Ahn, Wook; Lee, Dong Un; Li, Ge; Feng, Kun; Wang, Xiaolei; Yu, Aiping; Lui, Gregory; Chen, Zhongwei

    2016-09-28

    Highly oriented rGO sponge (HOG) can be easily synthesized as an effective anode for application in high-capacity lithium ion hybrid capacitors. X-ray diffraction and morphological analyses show that successfully exfoliated rGO sponge on average consists of 4.2 graphene sheets, maintaining its three-dimensional structure with highly oriented morphology even after the thermal reduction procedure. Lithium-ion hybrid capacitors (LIC) are fabricated in this study based on a unique cell configuration which completely eliminates the predoping process of lithium ions. The full-cell LIC consisting of AC/HOG-Li configuration has resulted in remarkably high energy densities of 231.7 and 131.9 Wh kg(-1) obtained at 57 W kg(-1) and 2.8 kW kg(-1). This excellent performance is attributed to the lithium ion diffusivity related to the intercalation reaction of AC/HOG-Li which is 3.6 times higher that of AC/CG-Li. This unique cell design and configuration of LIC presented in this study using HOG as an effective anode is an unprecedented example of performance enhancement and improved energy density of LIC through successful increase in cell operation voltage window.

  17. Parameterization and Estimation of Surrogate Critical Surface Concentration in Lithium-Ion Batteries (PREPRINT)

    DTIC Science & Technology

    2011-03-01

    1993), Modeling of Galvanostatic Charge and Discharge of the Lithium/ Polymer /Insertion Cell , Journal of Electrochemical Society, Vol.140, pp.1526-1533. P... Fuel Cells . Part I: Model Development, Journal of Electrochemical Society, Vol.145, pp.3407-3417. W. Gu, C. Wang, (2000), Thermal and Electrochemical...and the solid- electrolyte interface concentration of a surrogate single particle for each cell electrode. Equally-spaced radially-discretized diffusion

  18. High-performance lithium-ion battery and symmetric supercapacitors based on FeCo₂O₄ nanoflakes electrodes.

    PubMed

    Mohamed, Saad Gomaa; Chen, Chih-Jung; Chen, Chih Kai; Hu, Shu-Fen; Liu, Ru-Shi

    2014-12-24

    A successive preparation of FeCo2O4 nanoflakes arrays on nickel foam substrates is achieved by a simple hydrothermal synthesis method. After 170 cycles, a high capacity of 905 mAh g(-1) at 200 mA g(-1) current density and very good rate capabilities are obtained for lithium-ion battery because of the 2D porous structures of the nanoflakes arrays. The distinctive structural features provide the battery with excellent electrochemical performance. The symmetric supercapacitor on nonaqueous electrolyte demonstrates high specific capacitance of 433 F g(-1) at 0.1 A g(-1) and 16.7 F g(-1) at high scan rate of 5 V s(-1) and excellent cyclic performance of 2500 cycles of charge-discharge cycling at 2 A g(-1) current density, revealing excellent long-term cyclability of the electrode even under rapid charge-discharge conditions.

  19. 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.

  20. Three-Dimensional Carbon Nanotubes Forest/Carbon Cloth as an Efficient Electrode for Lithium-Polysulfide Batteries.

    PubMed

    Wu, Xiong-Wei; Xie, Hao; Deng, Qi; Wang, Hui-Xian; Sheng, Hang; Yin, Ya-Xia; Zhou, Wen-Xin; Li, Rui-Lian; Guo, Yu-Guo

    2017-01-18

    The development of a three-dimensionally flexible, large-surface area, high-conductivity electrode is important to improve the low conductivity and utilization of active materials and restrict the shuttle of long-chain polysulfides in Li-polysulfide batteries. Herein, we constructed an integrated three-dimensional carbon nanotube forest/carbon cloth electrode with heteroatom doping and high electrical conductivity. The as-constructed electrode provides strong trapping on the polysulfide species and fast charge transfer. Therefore, the Li-polysulfide batteries with as-constructed electrodes achieved high specific capacities of ∼1200 and ∼800 mA h g(-1) at 0.1 and 1 C, respectively. After 300 cycles at 0.5 C, a specific capacity of 623 mA h g(-1) was retained.

  1. Determining the sign of a polar surface of lithium niobate crystal by UV reflectance spectroscopy

    NASA Astrophysics Data System (ADS)

    Paranin, V. D.; Pantelei, E.

    2017-01-01

    We propose to reveal the + Z and- Z surfaces of a polar cut lithium niobate crystal by measuring its UV reflection spectrum. By the example of a congruent lithium niobate, it is shown that the intensities of light reflection from polar crystal surfaces of different signs in the region of 190—260 nm differ by up to several percent. The depth of short-wave radiation penetration into surface layers of the crystal in the spectral range of intrinsic absorption is estimated. It is shown that the proposed method can be used for determining the surface signs of polar crystal layers with thicknesses from several dozen to several hundred microns.

  2. 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.

  3. 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.

  4. Microfabrication of Surface Electrode Ion Traps for Quantum Information Experiments

    NASA Astrophysics Data System (ADS)

    Ge, Yufei; Labaziewicz, Jaroslaw; Antohi, Paul; Chuang, Isaac

    2008-03-01

    Surface electrode ion traps, while promising for large-scale quantum computation, have long been challenged by ion heating rates which increase rapidly as trap length scales are reduced. Through a series of measurements on over fifteen traps, we show that ion heating rates are surprisingly sensitive to electrode material and morphology, and in particular, to details of the fabrication procedure. For example, one 75 μm size trap, made of chemically etched silver on a single crystal quartz substrate, showed a minimum heating rate of ˜40 quanta/second, when prepared by annealing at 760^oC in vacuum for one hour. This annealing smooths sharp edges, and significantly reduces breakdown voltage. However, if the annealing temperature is lowered to 720^oC, leaving the breakdown voltage still robustly high, the heating rate jumps to ˜1000 quanta/second. With electroplated gold, on a silver seed layer, a record low heating rate of ˜2 quanta/second is obtained. We present details of the fabrication procedures, evaluate alternative electrode materials such as niobium nitride, and explain how these measurements were obtained with an ion trap operated at 6 Kelvin, containing a single strontium ion, sideband cooled to its quantum ground state of motion.

  5. Multifunctional Indium Tin Oxide Electrode Generated by Unusual Surface Modification

    NASA Astrophysics Data System (ADS)

    Bouden, Sarra; Dahi, Antoine; Hauquier, Fanny; Randriamahazaka, Hyacinthe; Ghilane, Jalal

    2016-11-01

    The indium tin oxide (ITO) material has been widely used in various scientific fields and has been successfully implemented in several devices. Herein, the electrochemical reduction of ITO electrode in an organic electrolytic solution containing alkali metal, NaI, or redox molecule, N-(ferrocenylmethyl) imidazolium iodide, was investigated. The reduced ITO surfaces were investigated by X-ray photoelectron spectroscopy and grazing incident XRD demonstrating the presence of the electrolyte cation inside the material. Reversibility of this process after re-oxidation was evidenced by XPS. Using a redox molecule based ionic liquid as supporting electrolyte leads to fellow electrochemically the intercalation process. As a result, modified ITO containing ferrocenyl imidazolium was easily generated. This reduction process occurs at mild reducing potential around ‑1.8 V and causes for higher reducing potential a drastic morphological change accompanied with a decrease of the electrode conductivity at the macroscopic scale. Finally, the self-reducing power of the reduced ITO phase was used to initiate the spontaneous reduction of silver ions leading to the growth of Ag nanoparticles. As a result, transparent and multifunctional active ITO surfaces were generated bearing redox active molecules inside the material and Ag nanoparticles onto the surface.

  6. Multifunctional Indium Tin Oxide Electrode Generated by Unusual Surface Modification

    PubMed Central

    Bouden, Sarra; Dahi, Antoine; Hauquier, Fanny; Randriamahazaka, Hyacinthe; Ghilane, Jalal

    2016-01-01

    The indium tin oxide (ITO) material has been widely used in various scientific fields and has been successfully implemented in several devices. Herein, the electrochemical reduction of ITO electrode in an organic electrolytic solution containing alkali metal, NaI, or redox molecule, N-(ferrocenylmethyl) imidazolium iodide, was investigated. The reduced ITO surfaces were investigated by X-ray photoelectron spectroscopy and grazing incident XRD demonstrating the presence of the electrolyte cation inside the material. Reversibility of this process after re-oxidation was evidenced by XPS. Using a redox molecule based ionic liquid as supporting electrolyte leads to fellow electrochemically the intercalation process. As a result, modified ITO containing ferrocenyl imidazolium was easily generated. This reduction process occurs at mild reducing potential around −1.8 V and causes for higher reducing potential a drastic morphological change accompanied with a decrease of the electrode conductivity at the macroscopic scale. Finally, the self-reducing power of the reduced ITO phase was used to initiate the spontaneous reduction of silver ions leading to the growth of Ag nanoparticles. As a result, transparent and multifunctional active ITO surfaces were generated bearing redox active molecules inside the material and Ag nanoparticles onto the surface. PMID:27857192

  7. Simultaneous electronic and ionic conduction in a block copolymer: application in lithium battery electrodes.

    PubMed

    Javier, Anna E; Patel, Shrayesh N; Hallinan, Daniel T; Srinivasan, Venkat; Balsara, Nitash P

    2011-10-10

    Charging ahead: separate values for the simultaneous electronic and ionic conductivity of a conjugated polymer containing poly(3-hexylthiophene) and poly(ethylene oxide) (P3HT-PEO) were determined by using ac impedance and dc techniques. P3HT-PEO was used as binder, and transporter of electronic charge and Li(+) ions in a LiFePO(4) cathode, which was incorporated into solid-state lithium batteries.

  8. 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.

  9. Direct synthesis of trirutile-type LiMgFeF6 and its electrochemical characterization as positive electrode in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lieser, Georg; Dräger, Christoph; de Biasi, Lea; Indris, Sylvio; Geßwein, Holger; Glatthaar, Sven; Hoffmann, Michael J.; Ehrenberg, Helmut; Binder, Joachim R.

    2015-01-01

    The energy density of lithium-ion batteries can be raised by increasing the redox potential of the positive electrode. This can be done in principle by substituting oxygen in commonly used lithium transition metal oxides with the more electronegative fluorine. To synthesize the quaternary lithium transition metal fluoride LiMgFeF6 with triturile structure a sol-gel process without toxic chemicals was used. The as-synthesized LiMgFeF6 was ball milled with carbon and binder to characterize the electrochemical properties of the LiMgFeF6/carbon/binder nanocomposite against lithium metal. After 20 cycles of galvanostatic cycling a reversible specific capacity of 107 mAh g-1, which is 80% of the theoretical capacity (1 eq. Li = 133 mAh g-1), was retained. In a rate performance test up to a discharge rate of 1C the LiMgFeF6/carbon/binder nanocomposite provided a specific capacity of 64 mAh g-1. Moessbauer spectroscopy and cyclic voltammetry confirmed the electrochemically active redox couple Fe3+/Fe2+ during cycling against lithium metal. Structural changes of the trirutile structure after lithium insertion have been investigated by X-ray powder diffraction.

  10. 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.

  11. The role of SEI in lithium and lithium ion batteries

    SciTech Connect

    Peled, E.; Golodnitsky, D.; Ardel, G.; Menachem, C.; Bar-Tow, D.; Eshkenazy, V.

    1995-12-31

    This paper presents and discusses fundamental processes taking place at the lithium and Li{sub x}C{sub 6} electrode/electrolyte interphases and models for these interphases. The authors deal with both nonaqueous and polymer (dry and gel) electrolytes, graphitized and nongraphitized carbonaceous materials as anodes for Li-ion batteries. Each electrode/electrolyte combination has its own unique features and problems but there are some general phenomena common to all of them. Issues to be reviewed include SEI composition, morphology and formation reactions, graphite surface modifications including chemical bonded SEI and micro channels formation, electrode degradation processes, lithium deposition-dissolution and intercalation-deintercalation mechanisms, rate-determining steps (RDS), electrolyte and electrode parameters and conditions affecting the above mentioned processes. Technology-related issues are emphasized.

  12. Double-plasma enhanced carbon shield for spatial/interfacial controlled electrodes in lithium ion batteries via micro-sized silicon from wafer waste

    NASA Astrophysics Data System (ADS)

    Chen, Bing-Hong; Chuang, Shang-I.; Duh, Jenq-Gong

    2016-11-01

    Using spatial and interfacial control, the micro-sized silicon waste from wafer slurry could greatly increase its retention potential as a green resource for silicon-based anode in lithium ion batteries. Through step by step spatial and interfacial control for electrode, the cyclability of recycled waste gains potential performance from its original poor retention property. In the stages of spatial control, the electrode stabilizers of active, inactive and conductive additives were mixed into slurries for maintaining architecture and conductivity of electrode. In addition, a fusion electrode modification of interfacial control combines electrolyte additive, technique of double-plasma enhanced carbon shield (D-PECS) to convert the chemical bond states and to alter the formation of solid electrolyte interphases (SEIs) in the first cycle. The depth profiles of chemical composition from external into internal electrode illustrate that the fusion electrode modification not only forms a boundary to balance the interface between internal and external electrodes but also stabilizes the SEIs formation and soothe the expansion of micro-sized electrode. Through these effect approaches, the performance of micro-sized Si waste electrode can be boosted from its serious capacity degradation to potential retention (200 cycles, 1100 mAh/g) and better meet the requirements for facile and cost-effective in industrial production.

  13. 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.

  14. Phase-field modeling of stress generation in electrode particles of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Huttin, Magalie; Kamlah, Marc

    2012-09-01

    Many cathode materials in lithium ion batteries show capacity fade due to particle crackings even at low applied charge and discharge current (C-rate). The promising candidate material LixMn2O4 exhibits such effects on the 4 V-plateau when the state of charge 0

  15. Layered amorphous silicon as negative electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Leyi; Dvorak, D. J.; Obrovac, M. N.

    2016-11-01

    Chemical delithiation is used to prepare bulk quantities of amorphous silicon powder from lithium-silicon compounds. The amorphous silicon materials formed are air and water stable and are found to have layered structures. When cycled in Li-ion half cells, coatings containing layered amorphous silicon are found to have significantly lower volume expansion during lithiation and improved cycling characteristics compared to that of bulk crystalline Si. We suggest chemical delithiation as a convenient method to synthesize bulk quantities of Si powders containing self-organized void spaces that can accommodate volume expansion during lithiation.

  16. Surface tension of aqueous lithium bromide solutions containing 1-octanol as a heat-transfer additive

    SciTech Connect

    Ishida, Kenji; Mori, Y.H.

    1996-11-01

    The surface tension of simulated heat-pump working fluids, aqueous solutions of lithium bromide containing 1-octanol, has been measured, for the first time using a recently developed technique (Ishida et al., Rev. Sci. Instrum. 64, 1,324 (1993)) which is inherently suitable for characterizing the surfactant solution surfaces from the aspects of thermodynamic adsorption equilibrium and adsorption kinetics. The measurement has revealed that even the highest-grade reagents of lithium bromide commercially available are not necessarily free from surfactant impurities. Obtained data on the surface tension vs 1-octanol concentration have been examined on the basis of an equilibrium adsorption model. Through the optimal fitting of the Langmuir-type surface equation of state to the data, they have calculated the surface tension vs surface excess relation and also the variation in surface tension vs 1-octanol concentration relation with the surface area per unit volume of a given solution.

  17. Structural phase transition and electrode characteristics of LiMn{sub 2{minus}x}Mg{sub x}O{sub 4} positive electrode material for the lithium secondary battery

    SciTech Connect

    Idemoto, Y.; Udagawa, K.; Koura, N.; Richardson, J. W., Jr.; Takeuchi, K.; Loong, C.-K.

    1999-12-10

    With in mind improving the cycle performance of 4V class lithium manganese oxide positive electrode material for the lithium secondary battery, the authors have been investigating the effects of partial substitution of Mn by another metal. The crystal phase transition in the quaternary spinel LiMn{sub 2{minus}x}Mg{sub x}O{sub 4} was studied by neutron powder diffraction at 200K and DSC measurements at low temperatures. They find that substituting Mn by Mg resulted in a more stable crystal structure with the Jahn-Teller transition suppressed down to low temperature. The charge-discharge characteristics of these positive electrode active materials were investigated at 4V range. Although the discharge capacity decreased with increasing Mg content, the cycle performance was improved with increasing Mg content.

  18. 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.

  19. Effect of surface modifiers on the electrode reactions and conformation of cytochrome c3 adsorbed on a silver electrode.

    PubMed

    Hobara, D; Niki, K; Cotton, T M

    1998-01-01

    Surface-enhanced resonance Raman scattering and electroreflectance voltammetry were used to investigate the effect of electrode surface modification on the structure and redox properties of cytochrome c3 immobilized on Ag surfaces. It is shown that the redox reactions of cytochrome c3 are more reversible at an 11-mercaptoundecanoic acid modified Ag electrode as compared to a bare metal surface. The heme of cytochrome c3 is in a mixed low and high spin state when adsorbed at the bare electrode, whereas only the low spin form is present on the 11-mercaptoundecanoic acid modified electrode, suggesting that the native conformation is maintained in the latter case. The reduction potential is close to that of the most positive macroscopic potential as determined by electroreflectance spectroscopy. In contrast, the reduction potential as determined by SERRS undergoes a large positive shift in the presence of 4,4'-bipyridine, the magnitude of which is dependent upon the concentration of 4,4'-bipyridine. These results indicate that the effect of the cytochrome c3 interaction with the 4,4'-bipyridine-modified surface is significantly different as compared to its interaction with the 11-mercaptoundecaodoic acid modified surface. Moreover, the results emphasize that electrode modifiers can have dramatically different effects on the redox properties of different proteins. It is well known that 4,4'-bipyridine acts as a redox promoter in the case of cytochrome c, whereas no electrochemical or electroreflectance response was observed in the case of cytochrome c3.

  20. 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.

  1. Charge-discharge characteristics of all-solid-state thin-filmed lithium-ion batteries using amorphous Nb 2O 5 negative electrodes

    NASA Astrophysics Data System (ADS)

    Nakazawa, Hiromi; Sano, Kimihiro; Abe, Takashi; Baba, Mamoru; Kumagai, Naoaki

    All-solid-state thin-filmed lithium-ion rechargeable batteries composed of amorphous Nb 2O 5 negative electrode with the thickness of 50-300 nm and amorphous Li 2Mn 2O 4 positive electrode with a constant thickness of 200 nm, and amorphous Li 3PO 4- xN x electrolyte (100 nm thickness), have been fabricated on glass substrates with a 50 mm × 50 mm size by a sputtering method, and their electrochemical characteristics were investigated. The charge-discharge capacity based on the volume of positive electrode increased with increasing thickness of negative electrode, reaching about 600 mAh cm -3 for the battery with the negative electrode thickness of 200 nm. But the capacity based on the volume of both the positive and negative electrodes was the maximum value of about 310 mAh cm -3 for the battery with the negative electrode thickness of 100 nm. The shape of charge-discharge curve consisted of a two-step for the batteries with the negative electrode thickness more than 200 nm, but that with the thickness of 100 nm was a smooth S-shape curve during 500 cycles.

  2. Template synthesis and characterization of nanostructured lithium insertion electrodes and nanogold/porous aluminum oxide composite membranes

    NASA Astrophysics Data System (ADS)

    Patrissi, Charles John

    A membrane-based template synthesis method was used to prepare nanostructured Li-ion battery electrodes and nanogold/porous aluminum oxide composite membranes. Membrane-based template synthesis is a general method for the preparation of nanomaterials which entails deposition of the material of interest, or a suitable precursor, within the nanometer-diameter pores in a porous template membrane. This method allows for control of nanoparticle size and shape and is compatible with many methods of synthesis for bulk materials. The template membranes used in this work were commercially available porous polycarbonate filtration membranes and nanoporous aluminum oxide membranes that were prepared in-house. Nanostructured electrodes of orthorhombic V2O5, prepared using membrane-based template synthesis, were used to investigate the effects of Li-ion diffusion distance and V2O5 surface area on electrode rate capability. Nanowires of V2O5 were prepared by depositing a precursor in the pores of microporous polycarbonate filtration membranes. The result was an ensemble of 115 nm diameter, 2 mum long nanowires of V2O5 which protruded from a V 2O5 surface layer like the bristles of a brush. The Li + storage capacity of the nanostructured electrode was compared to a thin film control electrode at high discharge rates. Results show that the nanostructured electrode delivered three to four times the capacity of the thin film electrode at discharge rates above 500 C. A membrane based template synthesis method was also used to prepare crystalline V2O5 electrodes which have high volumetric charge capacities, at high discharge rates, compared to a thin-film control electrode. In order to obtain high volumetric rate capability, the as-received polycarbonate template membranes were chemically etched to increase membrane porosity. Nanofibrous electrodes of crystalline V2O5 were then prepared by depositing an alkoxide precursor in the pores of the etched membranes. Electrode volumetric

  3. 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.

  4. 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.

  5. 3D macroporous electrode and high-performance in lithium-ion batteries using SnO2 coated on Cu foam.

    PubMed

    Um, Ji Hyun; Choi, Myounggeun; Park, Hyeji; Cho, Yong-Hun; Dunand, David C; Choe, Heeman; Sung, Yung-Eun

    2016-01-04

    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.

  6. 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

  7. Bulk-Type All-Solid-State Lithium-Ion Batteries: Remarkable Performances of a Carbon Nanofiber-Supported MgH2 Composite Electrode.

    PubMed

    Zeng, Liang; Ichikawa, Takayuki; Kawahito, Koji; Miyaoka, Hiroki; Kojima, Yoshitsugu

    2017-01-25

    Magnesium hydride, MgH2, a recently developed compound for lithium-ion batteries, is considered to be a promising conversion-type negative electrode material due to its high theoretical lithium storage capacity of over 2000 mA h g(-1), suitable working potential, and relatively small volume expansion. Nevertheless, it suffers from unsatisfactory cyclability, poor reversibility, and slow kinetics in conventional nonaqueous electrolyte systems, which greatly limit the practical application of MgH2. In this work, a vapor-grown carbon nanofiber was used to enhance the electrical conductivity of MgH2 using LiBH4 as the solid-state electrolyte. It shows that a reversible capacity of over 1200 mA h g(-1) with an average voltage of 0.5 V (vs Li/Li(+)) can be obtained after 50 cycles at a current density of 1000 mA g(-1). In addition, the capacity of MgH2 retains over 1100 mA h g(-1) at a high current density of 8000 mA g(-1), which indicates the possibility of using MgH2 as a negative electrode material for high power and high capacity lithium-ion batteries in future practical applications. Moreover, the widely studied sulfide-based solid electrolyte was also used to assemble battery cells with MgH2 electrode in the same system, and the electrochemical performance was as good as that using LiBH4 electrolyte.

  8. 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.

  9. Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

    PubMed

    Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

    2016-10-26

    Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNixMnyCo1-x-yO2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni(2+) (active) and Co(3+) (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive (7)Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the

  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. High-power lithium ion microbatteries from interdigitated three-dimensional bicontinuous nanoporous electrodes.

    PubMed

    Pikul, James H; Gang Zhang, Hui; Cho, Jiung; Braun, Paul V; King, William P

    2013-01-01

    High-performance miniature power sources could enable new microelectronic systems. Here we report lithium ion microbatteries having power densities up to 7.4 mW cm(-2) μm(-1), which equals or exceeds that of the best supercapacitors, and which is 2,000 times higher than that of other microbatteries. Our key insight is that the battery microarchitecture can concurrently optimize ion and electron transport for high-power delivery, realized here as a three-dimensional bicontinuous interdigitated microelectrodes. The battery microarchitecture affords trade-offs between power and energy density that result in a high-performance power source, and which is scalable to larger areas.

  12. Three-Dimensional Array of TiN@Pt3Cu Nanowires as an Efficient Porous Electrode for the Lithium-Oxygen Battery.

    PubMed

    Luo, Wen-Bin; Pham, Thien Viet; Guo, Hai-Peng; Liu, Hua-Kun; Dou, Shi-Xue

    2017-02-28

    The nonaqueous lithium-oxygen battery is a promising candidate as a next-generation energy storage system because of its potentially high energy density (up to 2-3 kW kg(-1)), exceeding that of any other existing energy storage system for storing sustainable and clean energy to reduce greenhouse gas emissions and the consumption of nonrenewable fossil fuels. To achieve high round-trip efficiency and satisfactory cycling stability, the air electrode structure and the electrocatalysts play important roles. Here, a 3D array composed of one-dimensional TiN@Pt3Cu nanowires was synthesized and employed as a whole porous air electrode in a lithium-oxygen battery. The TiN nanowire was primarily used as an air electrode frame and catalyst support to provide a high electronic conductivity network because of the high-orientation one-dimensional crystalline structure. Meanwhile, deposited icosahedral Pt3Cu nanocrystals exhibit highly efficient catalytic activity owing to the abundant {111} active lattice facets and multiple twin boundaries. This porous air electrode comprises a one-dimensional TiN@Pt3Cu nanowire array that demonstrates excellent energy conversion efficiency and rate performance in full discharge and charge modes. The discharge capacity is up to 4600 mAh g(-1) along with an 84% conversion efficiency at a current density of 0.2 mA cm(-2), and when the current density increased to 0.8 mA cm(-2), the discharge capacity is still greater than 3500 mAh g(-1) together with a nearly 70% efficiency. This designed array is a promising bifunctional porous air electrode for lithium-oxygen batteries, forming a continuous conductive and high catalytic activity network to facilitate rapid gas and electrolyte diffusion and catalytic reaction throughout the whole energy conversion process.

  13. 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.

  14. 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.

  15. 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

  16. TiO 2(B) as a promising high potential negative electrode for large-size lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Inaba, Minoru; Oba, Yasuyuki; Niina, Fumiharu; Murota, Yosuke; Ogino, Yasuyuki; Tasaka, Akimasa; Hirota, Ken

    Needle-like TiO 2(B) powder was obtained from K 2Ti 4O 9 precursor by ion exchange to protons, followed by dehydration. The charge and discharge characteristics of the TiO 2(B) powder were investigated as a high potential negative electrode in lithium-ion batteries. It had a high discharge capacity of 200-250 mAh g -1 at around 1.6 V vs. Li/Li +, which was comparable with that of TiO 2(B) nanowires and nanotubes prepared via a hydrothermal reaction in alkaline solution. It showed very good cycleability, and gave a discharge capacity of 170 mAh g -1 even in the 650th cycle. It also had a high rate capability, and gave a discharge capacity of 106 mAh g -1 even at 10 °C. In most of ethylene carbonate-based solutions, the TiO 2(B) powder exhibited good charge and discharge characteristics. However, it showed a poor compatibility with LiBF 4, propylene carbonate, and γ-butyrolactone. The TiO 2(B) powder showed good cycle performance in the presence of a non-flammable additive, trimethyl phosphate, up to 20 vol.%, and a high tolerance to water up to 1000 ppm. It was also found that inexpensive Al foil can be used as a current collector of the TiO 2(B) powder instead of Cu foil without sacrificing the performance.

  17. Heterogeneous TiO2/V2O5/Carbon Nanotube Electrodes for Lithium-Ion Batteries.

    PubMed

    Kurttepeli, Mert; Deng, Shaoren; Mattelaer, Felix; Cott, Daire J; Vereecken, Philippe; Dendooven, Jolien; Detavernier, Christophe; Bals, Sara

    2017-03-08

    Vanadium pentoxide (V2O5) is proposed and investigated as a cathode material for lithium-ion (Li-ion) batteries. However, the dissolution of V2O5 during the charge/discharge remains as an issue at the V2O5-electrolyte interface. In this work, we present a heterogeneous nanostructure with carbon nanotubes supported V2O5/titanium dioxide (TiO2) multilayers as electrodes for thin-film Li-ion batteries. Atomic layer deposition of V2O5 on carbon nanotubes provides enhanced Li storage capacity and high rate performance. An additional TiO2 layer leads to increased morphological stability and in return higher electrochemical cycling performance of V2O5/carbon nanotubes. The physical and chemical properties of TiO2/V2O5/carbon nanotubes are characterized by cyclic voltammetry and charge/discharge measurements as well as electron microscopy. The detailed mechanism of the protective TiO2 layer to improve the electrochemical cycling stability of the V2O5 is unveiled.

  18. Surface Acoustic Wave Non-Linear Interactions in Lithium Niobate.

    DTIC Science & Technology

    1983-01-01

    X and Y, Z lithium niobate were investigated for two different angles of interaction. The mixed frequency was at least 8. 5 dB weaker than the...Introduction ............................ 165 5.2 Results for Y,Z LiNb0 3 with w1/w,22.6o ........................ 0............ 166 5.3 Results for 38, X ...LiNbO 3 with 11/w20.41 .................................... 173 *5.14 Results for 38, X LiNbO3 with (-1/’ 2 2.44 .. . . . ...... .. .. ...... 179 i Vi

  19. 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

    2016-02-26

    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.

  20. 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

  1. 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.

  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.

  3. Tip surface changes in endocardial stimulation electrode, visualised by scanning electron microscopy.

    PubMed

    Hladky, M; Horn, V; Kamaryt, P; Cabanova, J; Zeman, K

    1975-01-01

    The authors have been probably the first investigators who applied scanning electron microscopy to studies of the changes occurring in the surface of the metalic tip of an endocardial stimulating electrode. They found a lowered conductivity for secondary electron emission, and describe the surface changes in a platiniridium-tipped electrode which had been used for almost four years, in comparison with an unused electrode.

  4. 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.

  5. Restructuring of an Ir(210) electrode surface by potential cycling.

    PubMed

    Soliman, Khaled A; Kolb, Dieter M; Kibler, Ludwig A; Jacob, Timo

    2014-01-01

    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.

  6. 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

  7. 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.

  8. Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation

    DOE PAGES

    Nicholas W. Brady; Takeuchi, Esther S.; Knehr, K. W.; ...

    2016-04-24

    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

  9. Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation

    SciTech Connect

    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.

    2016-04-24

    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. As a result, simulations capture the experimental differences in lithiation behavior between the first and second cycles.

  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. 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

  12. 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.

  13. Electrode and solid electrolyte thin films for secondary lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, C. H.; Kelder, E. M.; Schoonman, J.

    Electrostatic spray deposition (ESD) was employed to prepare thin layers of Li 1.2Mn 2O 4 (nominal composition) and BPO 4:0.035Li 2O for all-solid-state thin film lithium-ion batteries. The relationships between layer morphologies and deposition conditions such as solvent composition of the precursor solutions and substrate temperature were investigated. It was found that a low substrate temperature and/or high boiling point of the solvent may lead to a relatively dense structure. Reticular porous structures are formed, if films were deposited at 250°C and a mixture of 85 vol.% butyl carbitol and 15 vol.% ethanol was used as the solvent. The Li 1.2Mn 2O 4 layers, formed in the 250-400°C temperature range, were amorphous or micro-crystalline. After annealing beyond 600 °C, they could be crystallized into a spinel-structured material. Glassy BPO 4:0.035Li 2O layers could fill the pores of porous Li 1.2Mn 2O 4 layers to form a dense intermediate electrolyte layer. Thin-film rocking-chair batteries, Li 1.2Mn 2O 4|BPO 4:0.035Li 2O|Li 1.2Mn 2O 4|Al, were prepared and revealed an open-circuit voltage of about 1.2 V after charging.

  14. Two-dimensional V2O5 sheet network as electrode for lithium-ion batteries.

    PubMed

    Xu, Yun; Dunwell, Marco; Fei, Ling; Fu, Engang; Lin, Qianglu; Patterson, Brian; Yuan, Bin; Deng, Shuguang; Andersen, Paul; Luo, Hongmei; Zou, Guifu

    2014-11-26

    Two-dimensional V2O5 and manganese-doped V2O5 sheet network were synthesized by a one-step polymer-assisted chemical solution method and characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermal-gravimetric analysis, and galvanostatic discharge-charge analysis. The V2O5 particles were covered with thin carbon layers, which remained after decomposition of the polymer, forming a network-like sheet structure. This V2O5 network exhibits a high capacity of about 300 and 600 mA·h/g at a current density of 100 mA/g when it was used as a cathode and anode, respectively. After doping with 5% molar ratio of manganese, the capacity of the cathode increases from 99 to 165 mA·h/g at a current density of 1 A/g (∼3 C). This unique network structure provides an interconnected transportation pathway for lithium ions. Improvement of electrochemical performance after doping manganese could be attributed to the enhancement of electronic conductivity.

  15. Use of submicron carbon filaments in place of carbon black as a porous reduction electrode in lithium batteries with a catholyte comprising bromine chloride in thionyl chloride

    SciTech Connect

    Frysz, C.A.; Shui, X.; Chung, D.D.L.

    1995-12-31

    Submicron carbon filaments used in place of carbon black as porous reduction electrodes in carbon limited lithium batteries in plate and jellyroll configurations with the BCX (bromine chloride in thionyl chloride) catholyte gave a specific capacity (at 2 V cut-off) of up to 8,700 mAh/g carbon, compared to a value of up to 2,900 mAh/g carbon for carbon black. The high specific capacity per g carbon (demonstrating superior carbon efficiency) for the filament electrode is partly due to the filaments` processability into sheets as thin as 0.2 mm with good porosity and without a binder, and partly due to the high catholyte absorptivity and high rate of catholyte absorption of the filament electrode.

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

    SciTech Connect

    Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H.; Polzin, Bryant; Wang, Chong M.; Zhang, Jiguang; Xu, Wu

    2016-02-10

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

  17. Development of non-flammable lithium secondary battery with room-temperature ionic liquid electrolyte: Performance of electroplated Al film negative electrode

    NASA Astrophysics Data System (ADS)

    Ui, Koichi; Yamamoto, Keigo; Ishikawa, Kohei; Minami, Takuto; Takeuchi, Ken; Itagaki, Masayuki; Watanabe, Kunihiro; Koura, Nobuyuki

    The negative electrode performance of the electroplated Al film electrode in the LiCl saturated AlCl 3-1-ethyl-3-methylimizadolium chloride (EMIC) + SOCl 2 melt as the electrolyte for use in non-flammable lithium secondary batteries was evaluated. In the cyclic voltammogram of the electroplated Al film electrode in the melt, the oxidation and reduction waves corresponding to the electrochemical insertion/extraction reactions of the Li + ion were observed at 0-0.80 V vs. Li +/Li, which suggested that the electroplated Al film electrode operated well in the electrolyte. The almost flat potential profiles at about 0.40 V vs. Li +/Li on discharging were shown. The discharge capacity and charge-discharge efficiency was 236 mAh g -1 and 79.2% for the 1st cycle and it maintained 232 mAh g -1 and 77.9% after the 10th cycle. In addition, the initial charge-discharge efficiencies of the electroplated Al film electrode were higher than that of carbon electrodes. The main cathodic polarization reaction was the insertion of Li + ions, and side reactions hardly occurred due to the decomposition reaction of the melt because the Li content corresponding to the electricity was almost totally inserted into the film after charging.

  18. 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.

  19. Surface chemical analysis of CuO nanofiber composite electrodes at different stages of lithiation/delithiation

    NASA Astrophysics Data System (ADS)

    Gangaja, Binitha; Chandrasekharan, Sruthi; Vadukumpully, Sajini; Nair, Shantikumar V.; Santhanagopalan, Dhamodaran

    2017-02-01

    High aspect ratio, electrospun CuO nanofibers have been fabricated and tested for its electrochemical performance as lithium ion battery anode. These nanofibers are composed of CuO nanoparticles about 35-40 nm in size forming good inter-connected network. Fabricated half cells maintained specific capacity of 310 mAh g-1 at 1C rate for 100 cycles and stabilized capacity of about 120 mAh g-1 at 5C rate for 1000 cycles. Ex situ x-ray photoelectron spectroscopy (XPS) was performed to understand the electrodes surface chemical changes at the end of first discharge, first charge and after tenth charge. The solid electrolyte interface (SEI) layer comprised of LiF, Li2CO3 and Li2O while their quantity varied depending on the stage of lithiation/delithiation. Initially, no copper signal is observed on the surface of the SEI layer. However, in situ sputtering of the electrodes in the XPS chamber revealed that at the end of first discharge, formation Cu0 with detectable fraction of LixCuO2 and hydroxide in the SEI layer. At the end of first charge, a large fraction of Cu2O phase with a small fraction of hydroxide is observed. At the end of 10th charge no change in SEI layer content but increase in thickness was observed.

  20. Surface Response of Lithium Coatings on High Z Refractory Metal under Deuterium And Helium Ion Bombardment

    NASA Astrophysics Data System (ADS)

    Neff, Anton L.

    Lithium has proven to be a very interesting plasma facing component (PFC) material. It has been used as a wall coating in multiple research tokamaks, and at many of these facilities, lithium has improved confinement time by reducing hydrogen recycling from the walls of the reactor. Tungsten is also being considered as a durable PFC for fusion environments. The International Tokamak Experimental Reactor (ITER) will use a full tungsten divertor. Many operating tokamaks are using ITER like walls for testing ITER designs. From these tests and from controlled experiments, tungsten has shown some detrimental material changes under low energy deuterium and helium ion irradiation. Some of these material defects are holes, bubbles, voids, and fuzz. Because of the use of lithium in a number of tokamaks and the use of tungsten in many test reactors as well, studies have begun to study the behavior of lithium on the refractory metal tungsten. These studies deposited 100 and 500 nm of lithium on commercial tungsten discs and irradiated them with 100 eV deuterium, 1 keV helium, and deuterium and helium from two separate ion guns. The thicknesses of the lithium layers were determined by the temperature of the evaporator, over time, entered into a model using the Knudsen equation combined with an effusion model. This model was verified using AFM scans and SEM cross section micrographs of lithium layers on silicon substrates. Irradiations were carried out to a medium deuterium fluence of (1-3)x1017 D+/cm2. The surface chemistry of the samples before, after, and during irradiation was characterized using x-ray electron spectroscopy (XPS) in situ. These studies show that lithium on tungsten retains deuterium in a similar manner as does lithium on carbon; however, when helium is a secondary ion during irradiation, it can inhibit the deuterium retention in the lithium. In addition, the lithium is not eroded from the surface of the tungsten at the fluences that were achieved is this

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

    PubMed

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

    2014-03-27

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

  2. Surface analysis of supercapacitor electrodes after long-lasting constant current tests

    NASA Astrophysics Data System (ADS)

    Jänes, Alar; Eskusson, Jaanus; Lust, Enn

    2013-12-01

    FIB-SEM, XPS, TOF-SIMS and electrochemical methods have been used for the characterisation of physical properties and chemical composition of microporous carbide derived carbon electrodes, prepared from TiC at 950 °C (noted as TiC-CDC) after 40000 charge/discharge cycles. Changes in surface chemical composition of TiC-CDC electrodes, includes partial contamination with reaction intermediates (F2, CHO-, CN-, organic radicals), and Al current collectors, like partial dissolution of Al from positively charged electrode and deposition of Al onto the negatively charged TiC-CDC electrode surface, have been analysed.

  3. 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.

  4. Synthesis and electrochemical performance of surface-modified nano-sized core/shell tin particles for lithium ion batteries.

    PubMed

    Schmuelling, Guido; Oehl, Nikolas; Knipper, Martin; Kolny-Olesiak, Joanna; Plaggenborg, Thorsten; Meyer, Hinrich-Wilhelm; Placke, Tobias; Parisi, Jürgen; Winter, Martin

    2014-09-05

    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.

  5. 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.

  6. 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.

  7. Cathode material for lithium batteries

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2013-07-23

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

  8. Cathode material for lithium batteries

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2015-01-13

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

  9. Surface-enhanced Raman scattering of single-walled carbon nanotubes on modified silver electrode.

    PubMed

    Hou, Xiaomiao; Fang, Yan

    2008-04-01

    A roughed silver electrode modified with gold/silver nanoparticles is used as a substrate, on which high quality SERS of SWCNTs are obtained, indicating that the modified silver electrode is a high-quality SERS-active substrate for SWCNTs. Some new bands that indicate the structure of SWCNTs were obtained. The gold/silver nanoparticles modified on the roughed silver electrode surface can not only make sure the strong adsorption of SWCNTs in this system but also play an important role in magnifying the surface local electric field near the silver electrode surface through resonant surface plasmon excitation. From the rich information on the modified silver electrode obtained from the SERS and the potential dependent SERS, we may deduce the probable SERS mechanism in the process. The theory and experiment results indicate that it is can be used as a new technique for monitoring synthesis quality of SWCNTs. The probable reasons are given.

  10. Study of reversible electrode reaction and mixed ionic and electronic conduction of lithium phosphate electrolyte for an electrochemical CO2 gas sensor

    NASA Astrophysics Data System (ADS)

    Lee, Chong-Hoon

    An electrochemical CO2 gas sensor with lithium ion conductor was developed and characterized in order to examine the potential for real-life applications and understand its sensing mechanism. Li2CO3 and Li2TiO3 + TiO2 mixture were used as a sensing and a reference auxiliary phase, respectively. This electrochemical cell with a solid state Li3PO4 electrolyte has shown good selectivity, sensitivity and linear response in laboratory and automobile exhaust tests. However, the sensor response to CO2 gas showed a systematic deviation from the Nernst equation. Measured EMF did not agree with that calculated from the Nernst equation, even though it followed logarithmic behavior. Moreover, high sensitivity was observed for high CO2 concentrations (5˜50%), compared to that for concentrations (500˜5000 ppm). Two possible reasons for this deviation are: (1) reversibility of electrode reaction and (2) mixed ionic and electronic conduction of the electrolyte. Unless electrode reaction is fast enough, electrode polarization can easily induce overpotential. Pure ionic conduction of electrolyte is also necessary to avoid EMF loss during open circuit potential measurement. EIS (Electrochemical Impedance Spectroscopy) was used to study electrode kinetics. We found that Li2TiO3 + TiO2 mixture reference electrode reaction is sluggish showing large electrode impedance. This impedance, however, was not affected by gas concentration change. On the other hand, that at the Li2CO3 sensing electrode is relatively small and it increased with decreased CO2 and O 2 concentration. It was also observed that these electrode impedances induced the overpotential when the current flowed through the sensor. This electrode overpotential problem was minimized by mixing gold powder or porous sputtered gold electrode increasing effective reaction sites of the electrode. New electrode design improved the sensor EMF closer to the Nernstian values, however, the discrepancy still remained. Moreover, at

  11. Theoretical study of sorption and diffusion of lithium atoms on the surface of crystalline silicon and inside it

    NASA Astrophysics Data System (ADS)

    Kuzubov, A. A.; Eliseeva, N. S.; Popov, Z. I.; Fedorov, A. S.; Serzhantova, M. V.; Denisov, V. M.; Tomilin, F. N.

    2013-08-01

    The energy of the sorption and diffusion of lithium atoms on the reconstructed (4 × 2) (100) silicon surface in the process of their transport into near-surface layers, as well as inside crystalline silicon, at various lithium concentrations have been investigated within the density functional theory. It has been shown that single lithium atoms easily migrate on the (100) surface and gradually fill the surface states (T3 and L) located in channels between silicon dimers. The diffusion of lithium into near-surface silicon layers is hampered because of high potential barriers of the transition (1.22 eV). The dependences of the binding energy, potential barriers, and diffusion coefficient inside silicon on distances to the nearest lithium atoms have also been examined. It has been shown that an increase in the concentration of lithium to the Li0.5Si composition significantly reduces the transition energy (from 0.90 to 0.36 eV) and strongly increases (by one to three orders of magnitude) the lithium diffusion rate.

  12. 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.

  13. Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells

    SciTech Connect

    Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C.; Wu, Jinsong; Dravid, Vinayak P.; Yan, Pengfei; Wang, Chongmin; Kim, Soo; Wolverton, Christopher; Benedek, Roy; Dogan, Fulya; Park, Joong Sun; Croy, Jason R.; Thackeray, Michael M.

    2016-10-19

    Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3(1-x)LiMO2 (M=Ni, Mn, Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to manganese and nickel ions in close-packed oxides and (2) their higher potential (~3.6 V vs. Li0) relative to manganese oxide spinels (~2.9 V vs. Li0) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we have revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2 (0x0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2 structures, when prepared in air between 400 and 800 C, and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentration, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.

  14. Molecular layer deposition of "vanadicone", a vanadium-based hybrid material, as an electrode for lithium-ion batteries.

    PubMed

    Van de Kerckhove, Kevin; Mattelaer, Felix; Dendooven, Jolien; Detavernier, Christophe

    2017-03-08

    Molecular layer deposition (MLD) of hybrid organic-inorganic thin films called "vanadicones" was investigated using tetrakisethylmethylaminovanadium (TEMAV) as the metal precursor and glycerol (GL) or ethylene glycol (EG) as the organic reactant. Linear and continued growth could only be achieved with GL as the organic reactant. The TEMAV/GL process displayed self-limiting reactions for both precursor and reactant pulses in the temperature range from 80 °C to 180 °C, with growth rates of 1.2 to 0.5 Å per cycle, respectively. Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed the hybrid nature of the films. From X-ray reflectivity, the density was estimated at 2.6 g cm(-3). A series of 21 nm vanadicone films were subjected to annealing under oxidizing (air) or inert (He) atmospheres at 500 °C. During annealing in air, the film crystallized to the V2O5 phase and all carbon was removed from the film. The films annealed in helium remained amorphous and retained most of their carbon content. Electrochemical measurements revealed lithium-ion activity during cyclic voltammetry in all treated films, while the as deposited film was inactive. In the 2.9 to 3.5 V vs. Li(+)/Li potential region, no improvement over the V2O5 reference was observed. However, the helium annealed samples outperformed V2O5 in terms of capacity, rate performance and cyclability when charged and discharged in the 1.0 to 3.5 V vs. Li(+)/Li region. This result enables the application of VxOy-based hybrid electrodes in a wider potential range without sacrificing the stability and performance.

  15. Exploring Lithium-Cobalt-Nickel-Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells.

    PubMed

    Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C; Wu, Jinsong; Dravid, Vinayak P; Yan, Pengfei; Wang, Chongmin; Kim, Soo; Wolverton, Christopher; Benedek, Roy; Dogan, Fulya; Park, Joong Sun; Croy, Jason R; Thackeray, Michael Makepeace

    2016-10-04

    Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3●(1-x)LiMO2 (M=Ni, Mn, Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to manganese and nickel ions in close-packed oxides and (2) their higher potential (~3.6 V vs. Li(0)) relative to manganese oxide spinels (~2.9 V vs. Li(0)) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we have revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2 (0≤x≤0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2 structures, when prepared in air between 400 and 800 °C, and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentration, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.

  16. A Metal-Free, Free-Standing, Macroporous Graphene@g-C₃N₄ Composite Air Electrode for High-Energy Lithium Oxygen Batteries.

    PubMed

    Luo, Wen-Bin; Chou, Shu-Lei; Wang, Jia-Zhao; Zhai, Yu-Chun; Liu, Hua-Kun

    2015-06-01

    The nonaqueous lithium oxygen battery is a promising candidate as a next-generation energy storage system because of its potentially high energy density (up to 2-3 kW kg(-1)), exceeding that of any other existing energy storage system for storing sustainable and clean energy to reduce greenhouse gas emissions and the consumption of nonrenewable fossil fuels. To achieve high energy density, long cycling stability, and low cost, the air electrode structure and the electrocatalysts play important roles. Here, a metal-free, free-standing macroporous graphene@graphitic carbon nitride (g-C3N4) composite air cathode is first reported, in which the g-C3N4 nanosheets can act as efficient electrocatalysts, and the macroporous graphene nanosheets can provide space for Li2O2 to deposit and also promote the electron transfer. The electrochemical results on the graphene@g-C3N4 composite air electrode show a 0.48 V lower charging plateau and a 0.13 V higher discharging plateau than those of pure graphene air electrode, with a discharge capacity of nearly 17300 mA h g(-1)(composite) . Excellent cycling performance, with terminal voltage higher than 2.4 V after 105 cycles at 1000 mA h g(-1)(composite) capacity, can also be achieved. Therefore, this hybrid material is a promising candidate for use as a high energy, long-cycle-life, and low-cost cathode material for lithium oxygen batteries.

  17. Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode.

    PubMed

    David, L; Bhandavat, R; Barrera, U; Singh, G

    2015-04-08

    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.

  18. 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.

  19. X-ray absorption near-edge structure study on positive electrodes of degraded lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Shikano, Masahiro; Kobayashi, Hironori; Koike, Shinji; Sakaebe, Hikari; Saito, Yoshiyasu; Hori, Hironobu; Kageyama, Hiroyuki; Tatsumi, Kuniaki

    18650-type cylindrical cells using LiNi 1/3Mn 1/3Co 1/3O 2 (NMC) and hard carbon as positive and negative electrode material, respectively, were fabricated and degraded by cycle tests. The capacity of the cells remained more than 95% and 85% after cycle tests at 25 and 50 °C, respectively. After the cycle tests, Li-deficient cubic phase was observed on the surface of NMC. This phenomenon should be related to the degradation mechanism of this type of cell.

  20. Electrochemistry of chemically lithiated NaV{sub 3}O{sub 8}: A positive electrode material for use in rechargeable lithium-ion batteries

    SciTech Connect

    Spahr, M.E. |; Novak, P.; Scheifele, W.; Haas, O.; Nesper, R.

    1998-02-01

    Monoclinic NaV{sub 3}O{sub 8} was prepared via aqueous precipitation and subsequently chemically lithiated using butyllithium in hexane as lithiation reagent. The topochemical lithiation process leads to materials with variable lithium content depending on the lithiation reaction conditions. Up to 3 Li{sup +}/mol could be inserted chemically in the lattice water-free NaV{sub 3}O{sub 8} and result in cleavage of the particles, which leads to highly dispersed materials. In contrast to the chemical insertion method, almost 3.5 Li{sup +}/mol could be electrochemically inserted in NaV{sub 3}O{sub 8}, corresponding to a specific charge of about 310 mAh/g. About 2.5 Li{sup +}/mol could be deinserted potentiodynamically in the potential range from 1.5 to 4.0 V vs Li/Li{sup +} from a chemically lithiated material with the composition Li{sub 3}NaV{sub 3}O{sub 8}. This corresponds to a specific charge of about 215 mAh/g. In galvanostatic cycling experiments, a specific charge of more than 200 mAh/g could be demonstrated for 100 cycles using this electrode material. The specific charges obtained are independent of the applied specific current up to 50 mA/g of the oxide. This behavior indicates that the sodium vanadate host material can support high lithium insertion and deinsertion rates, which make the chemically lithiated form an attractive candidate for lithium-containing positive electrode materials in high-power lithium-ion batteries.

  1. Electrode

    SciTech Connect

    Clere, T.M.

    1983-08-30

    A 3-dimensional electrode is disclosed having substantially coplanar and substantially flat portions and ribbon-like curved portions, said curved portions being symmetrical and alternating in rows above and below said substantially coplanar, substantially flat portions, respectively, and a geometric configuration presenting in one sectional aspect the appearance of a series of ribbon-like oblate spheroids interrupted by said flat portions and in another sectional aspect, 90/sup 0/ from said one aspect, the appearance of a square wave pattern.

  2. Molten salt lithium cells

    DOEpatents

    Raistrick, Ian D.; Poris, Jaime; Huggins, Robert A.

    1983-01-01

    Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell (10) which may be operated at temperatures between about 100.degree.-170.degree. C. Cell (10) comprises an electrolyte (16), which preferably includes lithium nitrate, and a lithium or lithium alloy electrode (12).

  3. Molten salt lithium cells

    DOEpatents

    Raistrick, I.D.; Poris, J.; Huggins, R.A.

    1980-07-18

    Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400 to 500/sup 0/C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell which may be operated at temperatures between about 100 to 170/sup 0/C. The cell is comprised of an electrolyte, which preferably includes lithium nitrate, and a lithium or lithium alloy electrode.

  4. Molten salt lithium cells

    DOEpatents

    Raistrick, Ian D.; Poris, Jaime; Huggins, Robert A.

    1982-02-09

    Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and is operated in the temperature range of about 400.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems and a substantial amount of energy is lost through heat transfer. The present invention provides an electrochemical cell (10) which may be operated at temperatures between about 100.degree.-170.degree. C. Cell (10) comprises an electrolyte (16), which preferably includes lithium nitrate, and a lithium or lithium alloy electrode (12).

  5. 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.

  6. A Facile Electrophoretic Deposition Route to the Fe3O4/CNTs/rGO Composite Electrode as a Binder-Free Anode for Lithium Ion Battery.

    PubMed

    Yang, Yang; Li, Jiaqi; Chen, Dingqiong; Zhao, Jinbao

    2016-10-12

    Fe3O4 is regarded as an attractive anode material for lithium ion batteries (LIBs) due to its high theoretical capacity, natural abundance, and low cost. However, the poor cyclic performance resulting from the low conductivity and huge volume change during cycling impedes its application. Here we have developed a facile electrophoretic deposition route to fabricate the Fe3O4/CNTs (carbon nanotubes)/rGO (reduced graphene oxide) composite electrode, simultaneously achieving material synthesis and electrode assembling. Even without binders, the adhesion and mechanical firmness of the electrode are strong enough to be used for LIB anode. In this specific structure, Fe3O4 nanoparticles (NPs) interconnected by CNTs are sandwiched by rGO layers to form a robust network with good conductivity. The resulting Fe3O4/CNTs/rGO composite electrode exhibits much improved electrochemical performance (high reversible capacity of 540 mAh g(-1) at a very high current density of 10 A g(-1), and a remarkable capacity of 1080 mAh g(-1) can be maintained after 450 cycles at 1 A g(-1)) compared with that of commercial Fe3O4 NPs electrode.

  7. Effects of Surface Oxygen on the Performance of Carbon as an Anode in Lithium-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh; Clark, Gregory W.

    2001-01-01

    Carbon materials with similar bulk structure but different surface oxygen were compared for their performance as anodes in lithium-ion battery. The bulk structure was such that the graphene planes were perpendicular to the surface. Three types of surfaces were examined: surface containing C=O type oxygen. surface containing -O-C type oxygen, and surface containing high concentration of active sites. The test involved cycles of lithium insertion into and release from the carbon materials, which was in the half cells of carbon/saturated LiI-50/50 (vol %) EC and DMC/lithium. During the first cycle of lithium insertion, the presence of adsorbed oxygen, -O-C type oxygen, active carbon sites, and C=O type oxygen resulted in the formation of solid-electrolyte interface (SEI) when the carbon's voltage relative to lithium metal was >1.35, 1 to 1.35, 0.5 to 1, and 0.67 to 0.7 V, respectively. An optimum -O-C type oxygen and a minimum C=O type oxygen was found to increase the reversible and decrease the irreversible capacity of carbon. Active sites on the carbon surface result in a large irreversible capacity and a second lithium insertion-release mechanism. However, this new mechanism has a short cycle life.

  8. Flexible shrink-induced high surface area electrodes for electrochemiluminescent sensing.

    PubMed

    Pegan, Jonathan D; Ho, Adrienne Y; Bachman, Mark; Khine, Michelle

    2013-11-07

    Photolithographically defined metallic thin film on commodity shrink-wrap is leveraged to create robust electrodes. By thermally shrinking the film, electrodes are reduced by 20× in footprint for improved resolution and conductivity with >600% enhancements in electrochemically active surface area; as electrochemiluminescent sensors, they demonstrate improved limits of detection.

  9. Self-assembled sulfur/reduced graphene oxide nanoribbon paper as a free-standing electrode for high performance lithium-sulfur batteries.

    PubMed

    Liu, Yang; Wang, Xuzhen; Dong, Yanfeng; Tang, Yongchao; Wang, Luxiang; Jia, Dianzeng; Zhao, Zongbin; Qiu, Jieshan

    2016-10-25

    Flexible, interconnected sulfur/reduced graphene oxide nanoribbon paper (S/RGONRP) is synthesized through S(2-) reduction and evaporation induced self-assembly processes. The in situ formed sulfur atoms chemically bonded with the surface of reduced graphene oxide nanoribbons and were physically trapped by the compact assembly, which make the hybrid a suitable cathode material for lithium-sulfur batteries.

  10. Conducting Polymer Coated Graphene Oxide Electrode for Rechargeable Lithium-Sulfur Batteries.

    PubMed

    Lee, Hee-Yoon; Jung, Yongju; Kim, Seok

    2016-03-01

    Poly(diallyldimethylammonium chloride) (PDDA)/graphene oxide-sulfur composites were prepared by a chemical oxidation method. For the PDDA-GO composites, conducting polymers (PDDA) were coated on the surface of GO sheets. PDDA-GO composites could be expected to increase electrical conductivity and protect restacking of graphene sheets. And then, sulfur particles were dispersed into the PDDA-GO composites by mixing in the CS2 solvent. It is expected the PDDA-GO/S composites show the limited release of polysulfides due to the fact that it can provide high surface area, because conducting polymer can be used as spacer between graphene sheets. Electrochemical performances of prepared composites were characterized by cyclic voltammetry (CV). The PDDA-GO/S composites showed a high discharge capacity of 1102 mAh g(-1) at the first cycle and a good cycle retention of 60% after 100 cycles.

  11. Electrochemical oxidation of guanine: electrode reaction mechanism and tailoring carbon electrode surfaces to switch between adsorptive and diffusional responses.

    PubMed

    Li, Qian; Batchelor-McAuley, Christopher; Compton, Richard G

    2010-06-03

    The electrochemical oxidation of guanine is studied in aqueous media at various carbon electrodes. Specifically edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG), and highly ordered pyrolytic graphite (HOPG) were used, and the voltammetry was found to vary significantly. In all cases, signals characteristic of adsorbed guanine were seen and the total charge passed varied from surface to surface in the order roughened BPPG > EPPG > BPPG > HOPG. It is of note that the peak height for the EPPG electrode is less than that found for roughened BPPG; furthermore, across the series of electrodes, there is a significant decrease in peak potential with increasing density of edge plane sites present at the electrode surface. This leads us to conclude that there are two dominating and controlling factors present: (i) the density of basal plane sites on which guanine can adsorb and (ii) the density of edge plane sites necessary for the electro-oxidation of the analyte. This conclusion is corroborated through further experiments with multi- and single-walled carbon nanotubes. Adsorption was seen to be enhanced by modification of the EPPG surface with alumina particles, and as such, increased peak signals were observed in their presence. It is further reported that via the pre-adsorption of acetone onto the graphite surface that the adsorption of guanine may be blocked, resulting in a diffusional voltammetric signal. This diffusional response has been successfully modeled and gives insight into the complex -4e(-), -4H(+) oxidation mechanism; specifically, it enables explanation of the observed change in rate-determining step with scan rate. The oxidation of guanine first proceeds via a two-electron oxidation followed by a chemical step to form 8-oxoguanine, then 8-oxoguanine is then further oxidized to form nonelectroactive products. The change is mechanism is attributed to the variation in potential of the first and second electron transfer with scan

  12. Tin transition metal carbon alloys for lithium-ion battery negative electrodes

    NASA Astrophysics Data System (ADS)

    Todd, Andrew Douglas William

    Tin-transition metal (for M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) and tin-transition metal-carbon (for M = Ti, V and Co) alloys were studied using combinatorial materials science techniques and high throughput characterization methods to identify the optimum transition metal to use as an alloy for Li-ion battery negative electrodes. Amorphous composition ranges were found in the Sn-Ti, Sn-V, Sn-Cr, and Sn-Co systems with the amorphous range forming with the lowest concentration of transition metal for Co. No composition from the Sn-M systems showed stable charge-discharge cycling. Of the tin-transition metal-carbon alloys studied, it was determined that the Sn-Co-C system had compositions for which the charge-discharge cycling was stable and the specific capacities were close to 600 mAh/g. It is speculated that the Sn-Co-C system remains amorphous over many charge-discharge cycles because of a lack of stable, room temperature Co-carbides. Mossbauer effect spectroscopy was performed on a Sn1-xCo x library and a [Sn0.63Co0.37]1- yCy library to help understand the local environment of the tin atoms in these materials and it was determined that the carbon did not have a great effect. Small angle neutron scattering (SANS) measurements were used to compare Sn-Co-C materials produced by mechanical attriting to Sn-Co-C materials produced by sputter deposition. These results revealed differences in the nanostructure. The attrited [Sn0.5Co0.5]1- yCy (for y = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) materials were found to have a SnCo grain size on the order of 60 A while the sputtered [Sn0.45Co0.55 ]1-yCy (for y = 0.02, 0.10, 0.21, 0.34, 0.56, and 0.74) materials were found to be amorphous or have a SnCo grain size near 10 A, depending on composition. This difference in nanostructure may explain why the mechanically attrited samples could not attain their theoretical specific capacity while the sputtered samples were much closer to doing so. Porosity detected in the

  13. The Effect of Anodic Surface Treatment on the Oxidation of Catechols at Ultrasmall Carbon Ring Electrodes

    DTIC Science & Technology

    1991-07-09

    selectivity. A model of the surface formed following anodic oxidation is consistent with previous models involving both surface cleanliness and carbon...involving both surface cleanliness and carbon structure orientation. 2 INTRODUCTION Because of the vast electroanalytical utility of carbon electrodes...of the electron transfer rate following treatment are a function of the surface cleanliness and the orientation of the carbon structure

  14. Graphene Based Surface Plasmon Polariton Modulator Controlled by Ferroelectric Domains in Lithium Niobate

    PubMed Central

    Wang, Hao; Zhao, Hua; Hu, Guangwei; Li, Siren; Su, Hang; Zhang, Jingwen

    2015-01-01

    We proposed a ferroelectric domain controlled graphene based surface plasmon polariton modulator. Ferroelectricity-induced electronic and optical property tuning of graphene by domain in lithium niobate was theoretically investigated considering both interband and intraband contributions of surface conductivity. With the corrected Sellmeier equation of lithium niobate, the propagation of transverse magnetic mode surface plasmon polaritons in an air/graphene/lithium niobate structure was studied when monolayer graphene was tuned by down polarization direction ferroelectric domain with different polarization levels. The length of the ferroelectric domain was optimized to be 90 nm for a wavelength of 5.0 μm with signal extinction per unit 14.7 dB/μm, modulation depth 474.1 dB/μm and figure of merit 32.5. This work may promote the study of highly efficient modulators and other ultra-compact nonvolatile electronic and photonic devices in which two-dimensional materials and ferroelectric materials are combined. PMID:26657622

  15. Assembly of Self-Cleaning Electrode Surface for the Development of Refreshable Biosensors.

    PubMed

    Zhu, Xiaoli; Chen, Yaoyao; Feng, Chang; Wang, Wei; Bo, Bing; Ren, Ruixin; Li, Genxi

    2017-04-04

    Passivation of electrode surface and tedious reconstruction of biosensing architectures have long plagued researchers for the development of electrochemical biosensors. Here, we report a novel self-cleaning electrode by modifying the commonly used working electrode with superhydrophobic and conductive nanocomposite. Owing to the superhydrophobicity and the chemical stability, the electrode avoids passivation result from both adsorption of molecules and oxidation in air. The high conductivity and the high effective area also allow the achievement of enhanced electrochemical signals. On the basis of comprehensive studies on this novel electrode, we have applied it in the fabrication of refreshable electrochemical biosensors for both electro-active and electro-inactive targets. For both cases, detection of the targets can be well performed, and the self-cleaning electrode can be refreshed by simply washing and applied for successive measurements in a long period.

  16. 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.

  17. 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.

  18. Development of Nanoporous Carbide-Derived Carbon Electrodes for High-Performance Lithium-Ion Batteries

    DTIC Science & Technology

    2011-09-01

    exceptionally high surface area [11]. SiC Silicon Carbide Nb2C Niobium Carbide TiC Titanium Carbide NbC Niobium Carbide Mo2C Molybdenum Carbide SrC2...its electrochemical performance. Studies were conducted on three titanium carbide (TiC)-based CDC powders, synthesized at 600, 1000, and 1200 °C...were conducted on three titanium carbide (TiC)-based CDC powders, synthesized at 600, 1,000, and 1,200 °C. Custom-made CDC anodes were fabricated

  19. Electrochemical properties of lithium air batteries with Pt100-xRux (0 ≤ x ≤ 100) electrocatalysts for air electrodes

    NASA Astrophysics Data System (ADS)

    Yui, Yuhki; Sakamoto, Shuhei; Nohara, Masaya; Hayashi, Masahiko; Nakamura, Jiro; Komatsu, Takeshi

    2017-02-01

    Electrochemical properties of lithium air secondary battery cells with Pt100-xRux (0 ≤ x ≤ 100) electrocatalysts, prepared by the formic acid reduction method and loaded into air electrodes were examined in 1 mol/l LiTFSA/TEGDME electrolyte solution. Among the cells, the one with the Pt10Ru90 (x = 90)/carbon sample showed the largest discharge capacity of 1014 mAh/g and the lowest average charge voltage of 3.74 V. In addition, the x = 90 sample showed comparatively good cycle stability with discharge capacity of over 800 mAh/g at the 8th cycle. As a result, x = 90 was confirmed to be the optimized composition as the electrocatalyst for the air electrode.

  20. 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%)

  1. Nature of the Surface-Exposed Cytochrome-Electrode Interactions in Electroactive Biofilms of Desulfuromonas acetoxidans.

    PubMed

    Alves, A; Ly, H K; Hildebrandt, P; Louro, R O; Millo, D

    2015-06-25

    Metal-respiring bacteria are microorganisms capable of oxidizing organic pollutants present in wastewater and transferring the liberated electrons to an electrode. This ability has led to their application as catalysts in bioelectrochemical systems (BESs), a sustainable technology coupling bioremediation to electricity production. Crucial for the functioning of these BESs is a complex protein architecture consisting of several surface-exposed multiheme proteins, called outer membrane cytochromes, wiring the cell metabolism to the electrode. Although the role of these proteins has been increasingly understood, little is known about the protein-electrode interactions and their impact on the performance of BESs. In this study, we used surface-enhanced resonance Raman spectroscopy in combination with electrochemical techniques to unravel the nature of the protein-electrode interaction for the outer membrane cytochrome OmcB from Desulfuromonas acetoxidans (Dace). Comparing the spectroelectrochemical properties of OmcB bound directly to the electrode surface with those of the same protein embedded inside an electroactive biofilm, we have shown that the surface-exposed cytochromes of Dace biofilms are in direct contact with the electrode surface. Even if direct binding causes protein denaturation, the biofilm possesses the ability to minimize the extent of the damage maximizing the amount of cells in direct electrical communication with the electrode.

  2. 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.

  3. Multilayer graphene electrodes for one-port surface acoustic wave resonator mass sensor

    NASA Astrophysics Data System (ADS)

    Leong, Ainan; Swamy, Varghese; Ramakrishnan, N.

    2017-02-01

    A one-port surface acoustic wave (SAW) resonator mass sensor composed of multilayer graphene (MLG) electrodes was investigated by the finite element method (FEM) and analyses were carried out to study the enhancement of sensitivity and the secondary effects caused by MLG electrodes on the performance of the resonator. Unlike metal electrodes, MLG electrode offers elastic loading to the contact surface, as evidenced by the increase in the surface velocity of the SAW device. In terms of the sensitivity of the mass sensor, MLG electrode showed the largest center frequency shift in response to a change in mass loading, as well as when used as a gas sensor to detect volatile organic compounds (VOCs). Also, MLG electrodes offered the least triple transit signal (TTS) and bulk acoustic wave (BAW) generations compared with Al and Au–Cr electrodes. Thus, the one-port SAW resonator with graphene electrodes not only possesses excellent performance characteristics but also gives rise to new opportunities in the development of highly sensitive mass sensors.

  4. Nanostructured TiO2/carbon nanosheet hybrid electrode for high-rate thin-film lithium-ion batteries.

    PubMed

    Moitzheim, S; Nimisha, C S; Deng, Shaoren; Cott, Daire J; Detavernier, C; Vereecken, P M

    2014-12-19

    Heterogeneous nanostructured electrodes using carbon nanosheets (CNS) and TiO2 exhibit high electronic and ionic conductivity. In order to realize the chip level power sources, it is necessary to employ microelectronic compatible techniques for the fabrication and characterization of TiO2-CNS thin-film electrodes. To achieve this, vertically standing CNS grown through a catalytic free approach on a TiN/SiO2/Si substrate by plasma enhanced chemical vapour deposition (PECVD) was used. The substrate-attached CNS is responsible for the sufficient electronic conduction and increased surface-to-volume ratio due to its unique morphology. Atomic layer deposition (ALD) of nanostructured amorphous TiO2 on CNS provides enhanced Li storage capacity, high rate performance and stable cycling. The amount of deposited TiO2 masks the underlying CNS, thereby controlling the accessibility of CNS, which gets reflected in the total electrochemical performance, as revealed by the cyclic voltammetry and charge/discharge measurements. TiO2 thin-films deposited with 300, 400 and 500 ALD cycles on CNS have been studied to understand the kinetics of Li insertion/extraction. A large potential window of operation (3-0.01 V); the excellent cyclic stability, with a capacity retention of 98% of the initial value; and the remarkable rate capability (up to 100 C) are the highlights of TiO2/CNS thin-film anode structures. CNS with an optimum amount of TiO2 coating is proposed as a promising approach for the fabrication of electrodes for chip compatible thin-film Li-ion batteries.

  5. 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.

  6. Numerical modelling of needle-grid electrodes for negative surface corona charging system

    NASA Astrophysics Data System (ADS)

    Zhuang, Y.; Chen, G.; Rotaru, M.

    2011-08-01

    Surface potential decay measurement is a simple and low cost tool to examine electrical properties of insulation materials. During the corona charging stage, a needle-grid electrodes system is often used to achieve uniform charge distribution on the surface of the sample. In this paper, a model using COMSOL Multiphysics has been developed to simulate the gas discharge. A well-known hydrodynamic drift-diffusion model was used. The model consists of a set of continuity equations accounting for the movement, generation and loss of charge carriers (electrons, positive and negative ions) coupled with Poisson's equation to take into account the effect of space and surface charges on the electric field. Four models with the grid electrode in different positions and several mesh sizes are compared with a model that only has the needle electrode. The results for impulse current and surface charge density on the sample clearly show the effect of the extra grid electrode with various positions.

  7. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

    PubMed Central

    Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

    2016-01-01

    Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

  8. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

    SciTech Connect

    Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

    2016-03-18

    Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm-2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.

  9. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

    DOE PAGES

    Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

    2016-03-18

    Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm-2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

  10. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

    NASA Astrophysics Data System (ADS)

    Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

    2016-03-01

    Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm-2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.

  11. LiNi 0.8 Co 0.2 O 2 -based high power lithium-ion battery positive electrodes analyzed by x-ray photoelectron spectroscopy: 2. Following 3 formation cycles

    SciTech Connect

    Haasch, Richard T.; Abraham, Daniel A.

    2016-12-01

    High-power lithium-ion batteries are rapidly replacing the nickel metal hydride batteries currently used for energy storage in hybrid electric vehicles. Widespread commercialization of these batteries for vehicular applications is, however, limited by calendar-life performance, thermal abuse characteristics, and cost. The Advanced Technology Development Program was established by the U.S. Department of Energy to address these limitations. An important objective of this program was the development and application of diagnostic tools that provide unique ways to investigate the phenomena that limit lithium-ion cell life, performance, and safety characteristics. This report introduces a set of six Surface Science Spectra xray photoelectron spectroscopy (XPS) comparison records of data collected from positive electrodes (cathode) harvested from cylindrically wound, 18650-type, 1 A h capacity cells. The cathodes included in this study are (1) fresh, (2) following three formation cycles, (3) following calendar-life test for 12 weeks at 40 C, 60% state-of-charge (SOC), (4) following calendar-life test for 8 weeks at 50 C, 60% SOC, (5) following calendar-life test for 8 weeks at 60 C, 60% SOC, and (6) following calendar-life test for 2 weeks at 70 C, 60% SOC.

  12. Introduction to a series of LiNi 0.8 Co 0.2 O 2 -based high-power lithium-ion battery positive electrodes analyzed by x-ray photoelectron spectroscopy

    SciTech Connect

    Haasch, Richard T.; Abraham, Daniel A.

    2016-12-01

    High-power lithium-ion batteries are rapidly replacing the nickel metal hydride batteries currently used for energy storage in hybrid electric vehicles. Widespread commercialization of these batteries for vehicular applications is, however, limited by calendar-life performance, thermal abuse characteristics, and cost. The Advanced Technology Development Program was established by the U.S. Department of Energy to address these limitations. An important objective of this program was the development and application of diagnostic tools that provide unique ways to investigate the phenomena that limit lithium-ion cell life, performance, and safety characteristics. This report introduces a set of six Surface Science Spectra xray photoelectron spectroscopy (XPS) comparison records of data collected from positive electrodes (cathode) harvested from cylindrically wound, 18650-type, 1 A h capacity cells. The cathodes included in this study are (1) fresh, (2) following three formation cycles, (3) following calendar-life test for 12 weeks at 40 C, 60% state-of-charge (SOC), (4) following calendar-life test for 8 weeks at 50 C, 60% SOC, (5) following calendar-life test for 8 weeks at 60 C, 60% SOC, and (6) following calendar-life test for 2 weeks at 70 C, 60% SOC.

  13. The effect of electrode surface roughness on the motional heating rate of electromagnetic trapped ions

    NASA Astrophysics Data System (ADS)

    Lin, Kuan-Yu; Low, Guang Hao; Chuang, Isaac

    Electric field noise is a major source of motional heating in trapped ion quantum computation. While it is well known that this noise is influenced by trap electrode geometry in patch potential and surface adsorbate models, this has only been analyzed for smooth surfaces. We investigate the dependence of electric field noise on the roughness of surface electrodes by deriving a Green's function describing this roughness, and evaluating its effects on adsorbate-surface binding energies. At cryogenic temperature, surface roughness is found to exponentially enhance or suppress heating rate, depending on the density distribution of surface adsorbates. Our result suggests that heating rates can be tuned over orders of magnitude by careful engineering of electrode surface profiles.

  14. Method of forming macro-structured high surface area transparent conductive oxide electrodes

    DOEpatents

    Forman, Arnold J.; Chen, Zhebo; Jaramillo, Thomas F.

    2016-01-05

    A method of forming a high surface area transparent conducting electrode is provided that includes depositing a transparent conducting thin film on a conductive substrate, where the transparent conducting thin film includes transparent conductive particles and a solution-based transparent conducting adhesive layer which serves to coat and bind together the transparent conducting particles, and heat treating the transparent conducting adhesion layer on the conductive substrate, where an increased surface area transparent conducting electrode is formed.

  15. Li K-edge X-ray absorption near edge structure spectra for a library of lithium compounds applied in lithium batteries

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Zuin, Lucia

    2017-01-01

    Lithium ion batteries (LIB) have achieved great success as energy supply systems in portable devices and in electrical vehicles. Identifying the local chemical structures of elemental lithium in lithium compounds is beneficial for improving understanding of battery components and performance. Herein, a library of Li K-edge X-ray absorption near edge structure (XANES) of lithium compounds relevant to Li-ion batteries is reported. Materials described include lithium metals (anode), Li-containing cathodes, electrolytes and solid electrolyte interphase (SEI). The results illustrate the characteristic spectral features stemming from the various electronic structures and chemical environment of lithium atoms for each and every possible battery component. XANES spectra of Sn based anode after discharging reveal the appearance of Li2CO3 on electrode surface. X-ray damage on sensitive lithium species is also assessed; the results reveal that more attention should be paid to irradiation effects to conduct XANES measurements for battery materials properly.

  16. The Influence of Electrode Microstructure on the Performance of Free-Standing Cathode for Aprotic Lithium-Oxygen Battery

    NASA Astrophysics Data System (ADS)

    Shen, Chen; Wen, Zhaoyin; Wang, Fan; Wu, Xiangwei; Chen, Chunhua

    2016-10-01

    Free-standing NiCo2O4@Ni cathodes for aprotic lithium-oxygen batteries were synthesized through a simple hydrothermal process followed by heat treatment in the air. The morphology of the NiCo2O4 deposit changed from nanosheet to nanowire with the increase of hydrothermal time. Further observation revealed that the nanosheet/nanowire NiCo2O4 were assembled by nanoparticles with a size of 10-20 nm. The directional assembly of the nanoparticles were not affected by the reaction time. The influence of catalyst microstructure on the electrochemical performance of Li-O2 batteries was studied. The results of battery tests in pure oxygen indicate that the cathode material with a high specific surface area, large pore volume and broad pore size distribution can facilitate the discharge reaction, leading to an improved cell performance. As a result, the cathode based on the NiCo2O4 nanowire array delivered a specific discharge capacity of 1682 mAh g-1 at 30 mA g-1 and a stable cyclability of 50 cycles with a capacity limitation of 500 mAh g-1.

  17. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    SciTech Connect

    Bosch, Mathieu; Zhang, Muwei; Feng, Dawei; Yuan, Shuai; Wang, Xuan; Chen, Ying-Pin; Zhou, Hong-Cai

    2014-12-01

    Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs) showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in (Li [In(1,3 − BDC){sub 2}]){sub n} and enhancement of the H{sub 2} uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  18. Low surface area graphene/cellulose composite as a host matrix for lithium sulphur batteries

    NASA Astrophysics Data System (ADS)

    Patel, Manu U. M.; Luong, Nguyen Dang; Seppälä, Jukka; Tchernychova, Elena; Dominko, Robert

    2014-05-01

    Graphene/cellulose composites were prepared and studied as potential host matrixes for sulphur impregnation and use in Li-S batteries. We demonstrate that with the proper design of a relatively low surface area graphene/cellulose composite, a high electrochemical performance along with good cyclability can be achieved. Graphene cellulose composites are built from two constituents: a two-dimensional electronic conductive graphene and cellulose fibres as a structural frame; together they form a laminar type of pore. The graphene sheets that uniformly anchor sulphur molecules provide confinement ability for polysulphides, sufficient space to accommodate sulphur volumetric expansion, a large contact area with the sulphur and a short transport pathway for both electrons and lithium ions. Nano-cellulose prevents the opening of graphene sheets due to the volume expansion caused by dissolved polysulphides during battery operation. This, in turn, prevents the diffusion of lithium polysulphides into the electrolyte, enabling a long cycle life.

  19. Numerical and experimental evaluation of the relationship between porous electrode structure and effective conductivity of ions and electrons in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Inoue, Gen; Kawase, Motoaki

    2017-02-01

    This study aims to develop a correlation equation between a porous electrode structure and the effective conductivity so as to design an optimal structure for a thick electrode layer of a high-capacity battery. We carried out a three-dimensional reconstruction of a lithium cobalt oxide and graphite electrode based on the cross-sectional images obtained via focused ion beam-scanning electron microscopy (FIB-SEM). The Li ion and electron conductivities are evaluated based on the effective conductive path determined from simulation and these values are compared with the experimental results obtained by electrochemical impedance spectroscopy carries out with a symmetric cell and the direct conductivity measurement under compression. Moreover, the amount of binder and the diameter of the active material particles are increased and decreased numerically using an actual reconstructed electrode structure, and the effect of those structures on the effective conductivity is examined. The most dominant factors that degrade ionic conductivity are the binder distribution and the particle morphology, respectively, in the cathode and anode, and a correlation equation with the function of porosity is obtained. These values are compared with those obtained by theoretical model equations, and the difference between the current effective ionic conductivity and the physical limiting value is determined.

  20. Carbon-coated LiCrTiO4 electrode material promoting phase transition to reduce asymmetric polarization for lithium-ion batteries.

    PubMed

    Yang, Jianwen; Yan, Bo; Ye, Jing; Li, Xue; Liu, Yansheng; You, Haiping

    2014-02-21

    In this work, carbon-free and carbon-coated spinel LiCrTiO4 oxides were synthesized by a conventional solid state reaction. The lithium-ion diffusion coefficient and electronic conductivity of prepared electrode materials were systematically investigated using the galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The rate performances of the prepared materials were evaluated by galvanostatic charge-discharge. Carefully comparing the charge-discharge polarization potential of both materials, we unexpectedly discovered that the pristine LiCrTiO4 electrode demonstrated asymmetric polarization during the charging-discharging process, which is possibly attributed to the nonuniform electron conductivity between the endmember of a two-phase reaction, whereas carbon coating could level this phenomenon. Additionally, using an asymmetric core-shell model from the microscopic point of view can easily explain this common phenomenon. Meanwhile, this new research perspective can be extended to other active materials in lithium ion batteries.