WO2001091209A1 - Element de batterie electrochimique rechargeable dual a cations - Google Patents

Element de batterie electrochimique rechargeable dual a cations Download PDF

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Publication number
WO2001091209A1
WO2001091209A1 PCT/US2001/014681 US0114681W WO0191209A1 WO 2001091209 A1 WO2001091209 A1 WO 2001091209A1 US 0114681 W US0114681 W US 0114681W WO 0191209 A1 WO0191209 A1 WO 0191209A1
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WIPO (PCT)
Prior art keywords
cation species
battery cell
group
negative electrode
cation
Prior art date
Application number
PCT/US2001/014681
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English (en)
Inventor
Glenn Amatucci
Original Assignee
Telcordia Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Telcordia Technologies, Inc. filed Critical Telcordia Technologies, Inc.
Priority to EP01933137A priority Critical patent/EP1287569A1/fr
Priority to AU2001259584A priority patent/AU2001259584A1/en
Priority to JP2001587502A priority patent/JP2004513470A/ja
Publication of WO2001091209A1 publication Critical patent/WO2001091209A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a high voltage, high capacity rechargeable electrochemical battery cell which comprises a positive electrode, a negative electrode, and an interposed separator with an electrolyte comprising, during operation of the cell, a pair of different mobile cation species which individually participate in redox activity at the respective electrodes. More particularly, the invention relates to the preparation and use of a rechargeable battery cell comprising a polyvalent electrode material which participates predominantly, during cycling of the cell, in a redox reaction with the first of a pair of cation species, of which one is polyvalent, present in the cell electrolyte while the second of the cation species reacts predominantly at the opposite electrode of the cell .
  • These contemporary redox reactions enable multiple electron per ion transfer during cell operation with a resulting significant increase in cell capacity without loss of high voltage output.
  • lithium intercalation batteries particularly Li-ion cells
  • Li-ion cells which, by virtue of the light weight of the lithium electrode and electrolyte component materials, provide a significant level of specific capacity, i.e., the amount of energy per unit of cell weight that can be stored and transferred from a cell.
  • the high reactivity of lithium yields an additional benefit in providing an exceptionally low electrical potential in an incorporating negative cell electrode, which may comprise lithium metal or alloy, or a lithium-intercalating material.
  • metal oxide, sulfide, or fluoride materials are available which react with lithium at high electrical potential, thereby enabling their use as positive electrode components in resulting high-voltage battery cells.
  • An additional deterrent to the effective operation of a polyvalent ion cell is the passivation layer of reaction materials, referred to as a solid/electrolyte interface (SEI) , typically of reduction byproducts, e.g., electrolyte cation oxides, fluorides, carbonates, and the like, which form at the surface of the negative cell electrode during the first cycle charging period.
  • SEI solid/electrolyte interface
  • Li + ions of a common Li-ion intercalation cell are able to diffuse through the SEI layer in order to contact and be reduced at the negative electrode
  • polyvalent cations cannot diffuse in this manner and are significantly deterred from participating in the essential redox reaction at the negative electrode.
  • some reduction of the polyvalent cation may transpire, the reaction occurs at the invariably higher potential of the passivation layer reaction products, thus decreasing the potential difference between the electrodes with a resulting decrease in the operating cell voltage.
  • the practical utilization of polyvalent electrochemical cell components in order to increase cell capacity requires the implementation of a mechanism other than the simple transmission of a species of mobile polyvalent cation between cell electrodes.
  • the present invention provides such a novel and effective mechanism to enable the capacity-improving use of polyvalent cell components.
  • a rechargeable electrochemical cell prepared according to the present invention comprises a positive electrode member, a negative electrode member, and an interposed separator member which is ion-transmissive and electron-insulative. Also interposed and contained between the electrode members is an electrolyte comprising a polyvalent cation species, the electrolyte preferably being a non-aqueous solution of a solute providing polyvalent cations such as, e.g., Y 3+ , La 3+ , Mg 2+ , Ca 2+ , Ba 2+ , or Sr 2+ .
  • the positive electrode member comprises an active material, such as a transition metal oxide, sulfide, fluoride, or carbon fluoride, which can take up and release the polyvalent cation in a reversible oxidation reaction of intercalation, alloying, adsorption, or the like during operation of the cell.
  • the negative electrode member comprises an active material which provides a source of a second, highly reactive, negative-acting cation species, preferably of an alkali metal, such as Li + , Na + , K + , Rb + , or Cs + , capable of being reversibly released into and taken up from the electrolyte solvent during operation of the cell.
  • Such a negative electrode active material may be the alkali metal, an alloy of the alkali metal, or a carbonaceous material, e.g., coke, hard carbon, or graphite, capable of intercalating the alkali metal cation.
  • One embodiment of a cell of the present invention comprises a positive electrode member of V 2 O 5 , a negative electrode member of LiSi, and an electrolyte of 0.5 M Y(C10 ) 3 in a 2:1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) saturating a borosilicate glass fiber separator membrane.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Y 3+ ions from the electrolyte move to the reversible reaction at the positive electrode while Li + ions from the negative electrode are released into the EC:DMC solvent of the electrolyte. Due primarily to the physical proximity to the positive electrode of the relatively high concentration of Y 3+ ions and the higher overall potential of intercalation, these reactions predominate at their respective electrodes.
  • the reactions tend toward reversal in the usual manner, i.e., with deintercalation or other release of the Y 3+ ions from the positive electrode and movement of both cation species toward reduction at the negative electrode.
  • the rapid formation of passivation products at the surface of the negative electrode only the Li + ions are able to diffuse through the SEI layer in order to reach the LiSi negative electrode material where they are reduced at a potential of about that of the theoretical -3.0 V vs SHE.
  • the passivation layer at the negative electrode prevents the reduction of the Y 3+ ions, which remain in electrolyte solution, thus maintaining the low relative potential of the negative electrode and the resulting high operating voltage of the cell.
  • positive electrode members may be readily prepared by dispersing 28 parts of an active material capable of intercalating polyvalent cations, e.g., any of various vanadium oxides and cobalt oxides, preferably in nano-material form, with 6 parts conductive carbon in a matrix composition comprising an organic solution, e.g.
  • binder polymer such as a poly (vinylidene fluoride-co-hexafluoropropylene)
  • primary plasticizer for the polymer e.g., dibutyl phthalate.
  • the composition is cast as a layer which is air-dried to a membrane at room temperature prior to being cut to desired size for cell fabrication.
  • the membrane specimen may then be laminated to an electrically conductive current collector member and thereafter to counter-electrode and separator members.
  • the laminated assemblage is usually then extracted of incorporated plasticizer with a polymer-inert solvent, such as diethyl ether, prior to the addition of electrolyte solution.
  • FIG. 1 is a diagrammatic representation in cross section of a laminated battery cell embodying the present inventio ;
  • FIG. 2 is a graph tracing characteristic recycling voltage and specific capacity in a single monovalent cation cell of the prior art
  • FIG. 3 is a graph tracing characteristic recycling voltage and specific capacity in a single polyvalent cation cell
  • FIG. 4 is a graph tracing characteristic recycling voltage and specific capacity in one embodiment of a dual cation cell of the present invention.
  • FIG. 5 is a graph tracing characteristic recycling voltage and specific capacity in another embodiment of a dual cation cell of the present invention.
  • a battery cell structure 10 useful in the present invention comprises, preferably in the form of a laminated assembly of members such as described in the above- mentioned US Patent 5,460,904, a positive electrode member 13, a negative electrode member 17, and an interposed separator member 15 containing cell electrolyte.
  • Current collector members 11, 19 associated with the respective positive and negative electrode members provide electrical circuit connections for the cell, such as at extending terminal tabs 12, 16.
  • an intermediate electrode such as a silver wire 14, within separator member 15 in order to establish a quasi-reference electrical potential for the respective positive and negative half-cells.
  • positive electrode 13 comprises a vinylidene copolymer matrix membrane containing a dispersion of nano-sized active material, such as a transition metal oxide, e.g., V 2 0 5 , Mn0 2 , or Co 3 ⁇ 4 , capable of intercalating or adsorbing polyvalent electrolyte cations, for instance those of the alkaline earth group.
  • Negative counter-electrode 17 comprises a similar copolymer matrix dispersion of a nano-material compound, or simply a metal foil, capable of reversibly plating, alloying, intercalating, or otherwise reacting with, and thus providing a source of, monovalent cations, such as of Li, Na, or other alkali.
  • Separator 15 may likewise be a polymeric membrane, as described in the referenced specification, or it may comprise a widely used microporous membrane or simply a glass fiber mat, any of which is capable of absorbing the non-aqueous electrolyte, e.g., about a 0.5 to 2 M solution of a polyvalent cation compound in a solvent mixture of cyclic and acyclic carbonates.
  • Such an electrolyte may additionally comprise a small amount of a monovalent alkali salt which can benefit the reaction kinetics of the negative electrode and enable fabrication of the cell in the discharged state, as well.
  • Electrode 14 provides a convenient means for determining individually the electrolytic activity of selected composition constituents at the respective electrodes. In this manner, effective electrode and electrolyte combinations may be identified.
  • implementation of such a reference electrode was instrumental in confirming the electrolytic cell mechanism wherein a polyvalent cation species, e.g., Y 3+ , is denied access to a passivated alkali metal negative electrode and is thus unable to plate or reduce at that electrode in order to effect cell charging, despite applied voltages greatly in excess of that theoretically required.
  • a polyvalent cation species e.g., Y 3+
  • each test cell was arranged in circuit with a MacPile automatic cycling control/data-recording system operating in the galvanostatic mode at a preselected cycling rate of about 7.6 mA per g of active material to obtain a characteristic signature voltage/capacity profile of the test cell.
  • a lithium intercalation test cell was fabricated as a comparative example of the operating voltage level and capacity achieved in a single monovalent cation battery cell typical of the prior art.
  • a positive electrode was cast as a layer of a composition comprising 28 parts by weight of nano-sized V2O5, 6 parts of conductive carbon black (MMM super P) , 15 parts of poly (vinylidene fluoride-co-hexafluoropropylene) (Elf Atochem, Kynar 2801) , and 23 parts of dibutyl phthalate plasticizer in 28 parts of acetone.
  • the layer was dried at 22°C for about 0.5 hr to form a self-supporting membrane, and disks of 1 cm 2 were cut from the membrane to provide electrode members comprising about 4 to 10 mg of active material, i.e., V 2 0, 5 .
  • the plasticizer was extracted from the electrode disk member with diethyl ether.
  • a negative electrode member of LiSi was likewise prepared from a cast layer of a composition similar to that of the positive electrode, but for the substitution of Si for the V 2 O 5 .
  • a segment of the dried, extracted layer was overlaid upon a segment of lithium foil and an electrode member disk was cut from the composite material.
  • the LiSi alloy having a surface area of greater than about 0.5 m 2 /g spontaneously formed in situ at the electrode disk member over a short period of time.
  • the electrode members were assembled under substantially anhydrous conditions (-80°C dewpoint) in a Swagelok test cell with an intervening disk of borosilicate glass fiber mat saturated with a 1 M electrolyte solution of LiC10 4 in a 2:1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) .
  • the cell was then cycled in circuit with the automated test controller/recorder for a number of periods during which the Li + electrolyte cation reactions of intercalation at the positive electrode during discharge and reduction at the negative electrode during recharge were repeated in the usual manner.
  • the recorded data comprising the two-electrode output voltage of the cell and indicating a typical specific capacity of about 125 mAh/g, were plotted to yield the characteristic trace depicted in FIG. 2.
  • a second comparative example of a battery cell comprising a single polyvalent cation was prepared in the manner of Example I utilizing the positive electrode member of Example I and a negative electrode member comprising a nano-sized YSi 2 powder active material.
  • the electrolyte was a 0.5 M solution of Y(C10 ) 3 in the 2:1 mixture of EC: DMC.
  • Example III A battery cell embodying the present invention, i.e., comprising dual cations including at least one which is polyvalent, was prepared generally in the manner of the foregoing examples, comprising in the respective positive and negative electrodes materials capable of intercalating or adsorbing a polyvalent cation, such as that of yttrium, lanthanum, or an alkaline earth metal, during the discharge cycle segment and of reducing, plating, or alloying with the smaller and more reactive second cation, typically of a monovalent alkali, during the charging cycle segment.
  • the electrolyte provides the polyvalent cation and is capable of readily receiving into the electrolyte solution the second cation species .
  • the positive electrode member of this dual cation cell comprised the V0s nano-material of Example I and the negative electrode member comprised the LiSi of that example.
  • the active electrode materials of the cell may serve equally as well in the cell structure of the present invention as in those of the prior art, a surprisingly effective distinction is made in the electrolyte cation employed.
  • the cation of the electrolyte is selected to be the polyvalent cation of the dual cation combination while the complementary cation is typically the monovalent cation component of the negative electrode composition.
  • the electrolyte is a 0.5 M solution of Y(C10 4 ) 3 . A trace of the cycling voltage of the cell is depicted in FIG.
  • the theorized mode of operation of the dual cation cells of the present invention appears to follow the generalized process in which, during cell discharge, the polyvalent Y 3+ cations in the electrolyte solution are taken up at the positive electrode while Li + cations enter the solution from the negative electrode, and, during cell recharge, the Y 3+ polyvalent cation species reenters the electrolyte solution while the Li + cations are reduced and plated or alloyed at the negative electrode to maintain a stable low voltage cell datum at about -3 V vs SHE.
  • Example V Another embodiment of the dual cation cell of the invention was prepared with a negative electrode member of metallic lithium on a nickel support, a positive electrode member comprising a Co 3 0 4 active material, and a 0.5 M electrolyte solution of Y(C10 ) 3 . This cell provided results similar to the cell of Example III.
  • Example V
  • Yet another embodiment of the present invention was prepared with a negative electrode member of metallic sodium on a stainless steel support, a positive electrode member comprising a V2O 5 active material as in Example III, and a 0.33 M electrolyte solution of Y(CF 3 S0 3 ) 3 .
  • the trace of cycling characteristics of the cell as depicted in FIG. 5 confirms the high voltage stability and improved capacity of this cell of dual cation configuration.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Secondary Cells (AREA)
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Abstract

L'invention concerne un élément de batterie rechargeable (10) pourvu d'une tension de fonctionnement élevée et d'une capacité spécifique accrue considérablement, ledit élément comprenant un élément d'électrode positive (13), un élément d'électrode négative (17) et un élément de séparation interposé (15) renfermant un électrolyte contenant une solution d'un soluté de cations polyvalents dans un solvant non aqueux. L'élément d'électrode positive comprend une matière active qui prélève, de manière réversible, et libère l'espèce de cation polyvalent réactif pendant le fonctionnement de l'élément, tandis que la matière active de l'électrode négative libère de manière réversible une espèce de cation monovalent dans le solvant électrolytique et le prélève dudit solvant. Des espèces préférées de cations sont celles faisant partie des métaux terreux d'alcaline, tels que Y3+, et des métaux alcalins, tels que Li+.
PCT/US2001/014681 2000-05-24 2001-05-07 Element de batterie electrochimique rechargeable dual a cations WO2001091209A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP01933137A EP1287569A1 (fr) 2000-05-24 2001-05-07 Element de batterie electrochimique rechargeable dual a cations
AU2001259584A AU2001259584A1 (en) 2000-05-24 2001-05-07 Dual cation rechargeable electrochemical battery cell
JP2001587502A JP2004513470A (ja) 2000-05-24 2001-05-07 再充電可能なデュアルカチオン電気化学バッテリセル

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57764300A 2000-05-24 2000-05-24
US09/577,643 2000-05-24

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WO2001091209A1 true WO2001091209A1 (fr) 2001-11-29

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EP (1) EP1287569A1 (fr)
JP (1) JP2004513470A (fr)
KR (1) KR20030007651A (fr)
AU (1) AU2001259584A1 (fr)
TW (1) TW506154B (fr)
WO (1) WO2001091209A1 (fr)

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US8187752B2 (en) 2008-04-16 2012-05-29 Envia Systems, Inc. High energy lithium ion secondary batteries
US8389160B2 (en) 2008-10-07 2013-03-05 Envia Systems, Inc. Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials
US8394534B2 (en) 2009-08-27 2013-03-12 Envia Systems, Inc. Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling
US8465873B2 (en) 2008-12-11 2013-06-18 Envia Systems, Inc. Positive electrode materials for high discharge capacity lithium ion batteries
US8535832B2 (en) 2009-08-27 2013-09-17 Envia Systems, Inc. Metal oxide coated positive electrode materials for lithium-based batteries
US8663849B2 (en) 2010-09-22 2014-03-04 Envia Systems, Inc. Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries
US8741484B2 (en) 2010-04-02 2014-06-03 Envia Systems, Inc. Doped positive electrode active materials and lithium ion secondary battery constructed therefrom
US8765306B2 (en) 2010-03-26 2014-07-01 Envia Systems, Inc. High voltage battery formation protocols and control of charging and discharging for desirable long term cycling performance
US8871380B2 (en) 2010-07-30 2014-10-28 Nissan Motor Co., Ltd. Laminated battery
US8889287B2 (en) 2010-09-01 2014-11-18 Nissan Motor Co., Ltd. Bipolar battery
US8916294B2 (en) 2008-09-30 2014-12-23 Envia Systems, Inc. Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries
US8928286B2 (en) 2010-09-03 2015-01-06 Envia Systems, Inc. Very long cycling of lithium ion batteries with lithium rich cathode materials
US8993177B2 (en) 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
US9070489B2 (en) 2012-02-07 2015-06-30 Envia Systems, Inc. Mixed phase lithium metal oxide compositions with desirable battery performance
US9083062B2 (en) 2010-08-02 2015-07-14 Envia Systems, Inc. Battery packs for vehicles and high capacity pouch secondary batteries for incorporation into compact battery packs
US9159990B2 (en) 2011-08-19 2015-10-13 Envia Systems, Inc. High capacity lithium ion battery formation protocol and corresponding batteries
US9166222B2 (en) 2010-11-02 2015-10-20 Envia Systems, Inc. Lithium ion batteries with supplemental lithium
US9552901B2 (en) 2012-08-17 2017-01-24 Envia Systems, Inc. Lithium ion batteries with high energy density, excellent cycling capability and low internal impedance
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US9843041B2 (en) 2009-11-11 2017-12-12 Zenlabs Energy, Inc. Coated positive electrode materials for lithium ion batteries
US10056644B2 (en) 2009-07-24 2018-08-21 Zenlabs Energy, Inc. Lithium ion batteries with long cycling performance
US10115962B2 (en) 2012-12-20 2018-10-30 Envia Systems, Inc. High capacity cathode material with stabilizing nanocoatings
US10170762B2 (en) 2011-12-12 2019-01-01 Zenlabs Energy, Inc. Lithium metal oxides with multiple phases and stable high energy electrochemical cycling
US10290871B2 (en) 2012-05-04 2019-05-14 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
US11476494B2 (en) 2013-08-16 2022-10-18 Zenlabs Energy, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics

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JP2000133307A (ja) * 1998-10-21 2000-05-12 Matsushita Electric Ind Co Ltd 非水系二次電池

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JP2004513470A (ja) 2004-04-30

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