[go: up one dir, main page]

WO1998047195A1 - Technique permettant d'ameliorer une pile au lithium - Google Patents

Technique permettant d'ameliorer une pile au lithium Download PDF

Info

Publication number
WO1998047195A1
WO1998047195A1 PCT/US1998/007286 US9807286W WO9847195A1 WO 1998047195 A1 WO1998047195 A1 WO 1998047195A1 US 9807286 W US9807286 W US 9807286W WO 9847195 A1 WO9847195 A1 WO 9847195A1
Authority
WO
WIPO (PCT)
Prior art keywords
cell
carbon
lithium
thermally stable
negative electrode
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1998/007286
Other languages
English (en)
Inventor
Han Cheng Kuo
Ignacio Chi
Karthik Ramaswami
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Duracell Inc USA
Original Assignee
Duracell Inc USA
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 Duracell Inc USA filed Critical Duracell Inc USA
Priority to AU69665/98A priority Critical patent/AU6966598A/en
Publication of WO1998047195A1 publication Critical patent/WO1998047195A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 lithium ion rechargeable battery generally comprises a non-aqueous electrolyte in which a lithium salt is dissolved in a non-aqueous solvent and a positive electrode containing an active material which reacts with lithium.
  • the carbon anodes used in a re- chargeable lithium cell show exothermic reactivity with non-aqueous solvent electrolytes which are typically used in rechargeable cell system.
  • Lithium ion cells in the charged state tend to self heat when exposed to temperatures above 100°C. This reactivity is generally observed between temperatures of about 100°C to 150°C. It is believed that this self heating is caused by an exothermic reaction between the lithiated anode and the electrolyte. This exothermic activity leads to internal self heating and eventual failure of the cell. This could also cause the internal cell temperature to rise to unsafe levels where other exothermic processes may take place that could raise the temperature even higher. In a worst case scenario, a fire or explosion could conceivably ensue. It is an object of this invention to provide a process for increasing the thermal stability of a rechargeable lithium ion cell.
  • this invention contemplates a process for increasing the thermal stability of a electrochemical cell having a positive electrode, a lithium containing electrolyte salt dissolved in a non-aqueous solvent and a negative electrode which comprises a carbonaceous material, comprising the step of incorporating less than 5% by weight of carbon black into the negative electrode.
  • the process of this invention is applicable to a cell which comprises a positive electrode, a negative electrode, and a lithium containing electrolyte salt dissolved in a non-aqueous solvent.
  • the process comprises incorporating carbon black into a carbonaceous anode in an amount of less than 5% based on the combined weight of the carbon black, the binder and of any other carbon in the anode; forming a cell; and charging.
  • the anode is a synthetic or natural graphite carbon containing less than 5%, by weight, of carbon black.
  • the cathode is a lithiated metal oxide
  • the electrolyte salt is lithium hexafluorophosphate
  • the solvent is a mixture of ethylene carbonate with other linear organic carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and the like.
  • the cell is charged and then stored at a temperature of from about 45 °C to about 60°C for a period of time of from about one hour to about seventy-two hours. The storage improves the efficacy of the passivating layer which further increases the heat stability of the rechargeable lithium cell which is formed thereby.
  • the negative electrode of the lithium ion cells of this invention is predominantly carbon. Any conventional form of carbon known to be useful for lithium ion cells may be used as active material in the negative electrode.
  • Suitable electrically conductive carbonaceous materials include synthetic or natural graphite, and pyrolysis residues of various carbonaceous materials such as pitches, coals, synthetic high polymers, natural high polymers, for example, wood, coconut shells, cellulosic materials (such as cellulose, regenerated cellulose, cellulose acetates), starch, protein, wool, lignin and rubber, and the like.
  • Suitable synthetic high polymers will desirably have a molecular weight of at least about 5,000, and preferably 10,000 to 1,000,000, or even higher.
  • polyacrylonitrile polyvinyl chloride; polyvinylidene chloride, polyvinyl alcohol, polybutadiene, polyethylene, polymethylvinylketone, polyphenylens (such as p-polyphenylene), polystyrene, polyacetylenes, polyimides such as polyimidazopyrroloneimide, polyamides, polybenzimidazoles, polysemi- carbazides, polybenzoxadinones, epoxy resins, furan resins and phenolic resins.
  • Polyarylacetylenes (such as polyphenychloracetylene) are also useful.
  • Arylacetylene polymers can be obtained by the methods described in "Polymer Bulletin", Vol. 2, pages 823-827 (1980) and “Polymer Journal", Vol. 11, page 813 (1979) and Vol. 13, page 301 (1981).)
  • Suitable pitches include petroleum pitch, coal tar pitch, wood tar pitch and rosin pitch.
  • Illustrative of coals are lignite, brown coal, sub-bituminous coal, bituminous coal and anthracite.
  • Suitable phenolic resin starting materials include novolak and resol resins.
  • suitable phenolic resins are phenol-formalin resins, cresol- formalin resins, phenol-furfural resins, resorcinol-formalin resins, and the like; as well as modified phenolic resins, such as tercondensation polymers of phenols, aldehydes and natural resins, and etherified phenolic resins.
  • Pyrolysis residues of the organic materials used in this invention can be produced by known pyrolysis methods. Pyrolysis or carbonization is ordinarily performed by heating or thermal treatment of the abovementioned organic materials in a manner known in the art and in an atmosphere of inert gas, such as nitrogen, to a temperature sufficiently high to bring about substantially complete thermal decomposition of non-carbon constituents of the organic material and partial graphitization of the carbon.
  • the pyrolysis residues may be in the form of film, fiber, fabrics (woven fabric and non-woven fabric), thin platelets, and powder.
  • the most preferred carbons used in the anode are pyrolysis residues known as mesophase microbeads, particularly those having a mean diameter of about 6 to 25 microns.
  • Meso-carbon microbeads can be obtained from starting materials such as coal tar, coal tar pitch, petroleum heavy oil (e.g. asphalt), and ethylene bottom oil, etc., by separating and refining the spheres in reaction solutions formed by treating at 350-450°C under pressure (ordinary pressure to 20 kg/cm 2 G).
  • Carbonized or graphitized meso-carbon microbeads can be obtained by reacting the resulting powder of meso-carbon microbeads in inert gas atmosphere to carbonize or to additionally graphitize.
  • carbonaceous starting materials such as coal tar is heated to give meso-carbon microbeads and coal tar pitch.
  • the coal tar pitch can be hydrogenated, then heated to give meso-phase pitch, atomized in inert gas atmosphere, or made spherical in solution to give meso-carbon microbeads or its carbonized or graphitized materials.
  • Meso-carbon microbeads reportedly have a laminar structure [Brooks and Taylor, Carbon 3, p. 195 (1965)], each layer is reportedly composed of condensed polycyclic aromatic compound [Zimmer and White, "Disinclination Structure in Carbonaceous Mesophase and Graphite", Aerospace Report (1976)].
  • this invention prefers to use spherical carbon materials as lithium carriers, there are no special restrictions to the particle size of said carbon materials.
  • Particle size is ordinarily 1-150 um, preferably 0.5-80 um.
  • Specific surface is ordinarily under 50 m 2 /g, preferably under 5 m 2 /g. There are various advantages of using these spherical carbon materials.
  • mesophase microbeads provide enhanced battery performance, such as output power density. It is believed that this improvement is caused by the greater active surface area provided by these materials. This provides a higher output power density, as when compared to fibrous carbon materials, which are also useful to a lesser degree, as described above.
  • the discharge capacity per unit volume (weight) is also increased when compared to fibrous carbon materials, because microbeads can be packed to a higher density. Also, by regulating particle size distribution of the microbeads, optimized packing is possible. This results in a further increase in the discharge capacity per unit volume.
  • the negative electrode will also contain a small amount of carbon black, an electrically conductive filler.
  • suitable, useful carbon black materials are carbonaceous materials having apparent bulk densities in excess of 80 g/1. These include furnace blacks and channel blacks. It is preferred that the carbon black material be Shawinigan Black (an acetylene black).
  • Other commercially available carbon blacks include those of the Cabot Corporation such as Elftex-12, Mogul-L, Regal 660-R, Vulcan XC-72R, Monarch-7000 and Sterling R (all furnace blacks).
  • Carbon blacks available from Columbian Corporation include Neo Spectra AG and Royal Spectra (channel blacks) and Conductex-950 (furnace black).
  • the bulk densities of the aforementioned carbon blacks range from about 6-17 lb/ft 3 .
  • Materials such as Ketjenblack EC a highly conductive furnace black available from Noury Chemical Corporation with properties as described in Noury Chemical Corporation Bulletin No. 12-100 March, 1981) having much higher conductivities are also useful, but are not preferred.
  • the amount of carbon black may vary, but must be less than 5% by weight based upon the total weight of carbon, carbon black and binder in the negative electrode. When the amount of carbon black equals or exceeds 5 percent, the cell will be subject to the possibility of initiation of the undesirable exothermic activity discussed above. It is preferred, however, that the carbon black be present in an amount of from about 2% to about 4% because excellent results have thereby been obtained. Specifically, when about 3% carbon black is used in combination with the specific carbonaceous materials, electrolyte salts, and positive active electrode materials set forth herein, cell performance is enhanced while concomitantly avoiding the undesirable self-heating reactions discussed above.
  • the precise amount of carbon black that is used is carefully selected so that, when incorporated into the electrode, the surface area of the combined carbon particles therein (per gram of combined carbon black and mesophase bead carbon in the preferred embodiment) will be less than 5.0 m 2 /g. Most preferably, the amount of carbon black will be selected to provide a surface area of the combined carbon particles of between 3.9 and 4.8 m 2 /g. If there is too little carbon black present, the surface area of the combined carbon particles in the electrode will be below 3.9 m 2 /g. and the electrode will be inadequately active to provide a commercially acceptable cell. On the other hand, if there is too much carbon black present, the surface area of the combined carbon particles in the electrode will be above 5 m 2 /g.
  • the electrode will be subject to the undesirable rapid heat production which can pose an unnecessary risk. It is believed that by maintaining the surface area of the carbon mix under 5.0 m 2 /g the reactivity of the charged negative electrode with the electrolyte is reduced during thermal abuse, as tested, for example, by the UL 150°C Heating test.
  • a support for the carbon negative electrode is used, and will advantageously be selected from conductive foils or grids which can be of a metal such as nickel, copper, stainless steel, titanium, or the like.
  • the carbon is held on the support by a suitable binder such as a fluororesin, polyvinylidene fluoride, ethylene-propylene-diene terpolymer, styrene-butadiene rubber, carboxymethyl- cellulose, or the like.
  • Both electrodes require a binder, for example polyvinylidene fluoride, which is present in an amount of from about 1% to about 20% by weight of the active electrode material, and preferably from about 5% to about 10% by weight.
  • a conductive filler may also be present in the positive electrode in an amount of from about 1% to about 20% of the combined weight of the binder and the active electrode material.
  • the filler is preferably used in amounts of about 2% to about 5%.
  • the positive electrode of the cell is lithiated metal oxide. Any metal oxide capable of being lithiated can be used, such as titanium dioxide, nickel oxide, manganese dioxide, cobalt oxide, manganese oxide, or mixtures or complex salts thereof.
  • the lithiated metal oxide will advantageously be affixed to a support using a suitable binder.
  • the support to which the positive lithiated or lithiatable metal oxide electrode is affixed may be aluminum, aluminum alloys, titanium, stainless steel, and the like. Such supports are well known to those skilled in the art.
  • the electrolyte salt used in the cell is a lithium salt. Any lithium salt which does not adversely affect the performance or safety of the cell may be used.
  • the most preferred salt is lithium hexafluorophosphate (LiPF 6 ), other salts, such as, lithium tetrafluoroborate (LiBF 4 ); lithium trifluorosulfonamide (LiTFS), lithium trifluoromethane sulfonamide (LiTFSI) and the like and mixtures of two or more or the same are also useful. It is preferred however, that the electrolyte salt be lithium hexafluorophosphate or a mixture thereof with one of the other useful salts referred to above. Salts such as lithium hexafluoroar senate and lithium perchlorate should be avoided, because there are serious safety issues associated therewith, such as those discussed above.
  • the electrolyte salt is dissolved in a non-aqueous solvent.
  • the non- aqueous solvent may be selected from propylene carbonate, tetrahydrofuran, ethylene carbonate, diethyl carbonate, dimethoxy ethane, gamma butyrolactone, dimethyl carbonate, ethyl methyl carbonate, and the like and mixtures of two or more of the same.
  • the preferred solvent is a mixture of EC and DMC.
  • the electrolyte is generally dissolved in the solvent in an amount sufficient to constitute a solution which is from about 0.4 to about 2 Molar and preferably from 0.6 to about 1.5 Molar.
  • the separator between the negative and positive electrodes may be any suitable material such as a non- woven film of a synthetic resin such as polytetrafluoroethylene, polypropylene, polyethylene, or a woven porous body of such materials, or combinations forming multi-layer composites thereof.
  • the anode and cathode mixes (with a polymeric binder in appropriate liquid medium such as an organic solvent) in the form of a paste or slurry are separately coated onto a current collector grid, foil or mesh. This is then pressed into a sheet form, dried, cut to appropriate dimensions, and assembled with the remaining conventional elements into cells.
  • the cell will be stored to increase the efficacy of the passivating layer.
  • the passivating layer is the coating on the surface of the negative electrode which is formed as a result of a side reaction, during charging of the cell, between the lithium and the electrode.
  • the storage of a rechargeable lithium cell is described in copending application Serial No. 08/473,894, filed June 7, 1995 and entitled "Process For Improving Lithium Ion Cell".
  • the disclosure of application Serial No 08/473,894 is incorporated herein by reference thereto.
  • the charged lithium cell may be aged at a temperature of between about 20°C and about 75 °C for a period of time sufficient to increase the efficacy of the passivating layer.
  • the temperature at which the charged lithium cell is maintained will vary depending upon the non-aqueous solvent used, the electrolyte used, and the composition of the anode and the cathode. These compositional factors contribute to a determination of the optimum temperature and time at which the secondary lithium cell is stored.
  • Any rechargeable lithium cell may have the efficacy of its passivating layer increased to increase the heat stability of the cell by practicing the process for increasing efficacy of the passivating layer.
  • the cell In order to effectively increase the efficacy of the passivating layer, the cell, before being subjected to the process, must have been charged to more than 10% of its maximum acceptable charge. For example, after manufacture in the discharged state, the lithium cell will be charged, prior to practicing the process for increasing the passivating layer efficacy, to a partially or fully charged state. Full charge will generally be seen at about 4.0 to about 4.5 volts. It is also possible to partially charge as little as 10 percent of full charge. Preferably, the cell is charged to an intermediate voltage such as between 3.2 volts and about 4.5 volts and then the cell is aged.
  • an intermediate voltage such as between 3.2 volts and about 4.5 volts and then the cell is aged.
  • the cell may be fabricated into any suitable shape.
  • the anode and cathode, with a suitable separator material electrically isolating them from each other, is then wound into a tight cylindrical or prismatic "jelly roll" configuration and inserted into a cell can.
  • The, cell can is then filled with appropriate electrolyte, and crimp sealed or welded shut.
  • the cathode is prepared by mixing ninety parts of the positive active material which is lithiated cobalt oxide (LiCoO 2 ), with five parts of carbon black as conducting filler. A binder, TEFLON (PTFE) (5 parts), and isopropyl alcohol are added. The composition is mixed and then coated onto a collector which is an aluminum grid and formed into a sheet by and drying and cutting the resultant material.
  • the anode and cathode, with a separator (microporous polyethylene) electrically isolating them from each other are then wound into a tight cylindrical jelly roll configuration, and inserted into a cell can.
  • the cell can is then filled with IM LiPF 6 , in EC/DMC (in equal parts by volume) and then crimp sealed. The cell is then charged to 4.1V volts.
  • the fully charged cell is then cut open in a dry argon gas atmosphere, and the jelly roll is opened up.
  • the anode and cathode are then separated from each other, rolled up alone, and the anode is inserted into a fresh empty can of the same size as the original that had been cut open.
  • 1.0 cc of electrolyte IM LiPF 6 in EC/DMC is then added to the can which contains the anode.
  • the can is then crimp sealed exactly as an actual cell would be.
  • a thermocouple is welded to the external surface of the can to monitor the temperature.
  • the sealed can is then subjected to UL 150°C Oven Heating Test, which is a Standard test, exactly as if they were complete cells.
  • Electrodes are formed, and cells are constructed as in Example One ' ⁇ except that the anode is composed of eighty-eight parts of mesophase carbon micro beads, two parts of carbon black and ten parts of poly vinylidene fluoride.
  • the surface area of the combined carbon particles in the electrode is 3.93 m 2 /g.
  • the maximum temperatures reached for the cell is 172°C at 0.6 hour.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

On renforce la stabilité thermique d'une pile à ions lithium rechargeable en maintenant la teneur en noir de carbone de l'électrode négative inférieure à 5 % en poids et l'aire superficielle des particules combinées de carbone dans l'électrode entre 3,9 et 4,8 m2/g.
PCT/US1998/007286 1997-04-15 1998-04-10 Technique permettant d'ameliorer une pile au lithium Ceased WO1998047195A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU69665/98A AU6966598A (en) 1997-04-15 1998-04-10 Process for improving lithium ion cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84255697A 1997-04-15 1997-04-15
US08/842,556 1997-04-15

Publications (1)

Publication Number Publication Date
WO1998047195A1 true WO1998047195A1 (fr) 1998-10-22

Family

ID=25287625

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/007286 Ceased WO1998047195A1 (fr) 1997-04-15 1998-04-10 Technique permettant d'ameliorer une pile au lithium

Country Status (3)

Country Link
AU (1) AU6966598A (fr)
WO (1) WO1998047195A1 (fr)
ZA (1) ZA983067B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001091208A3 (fr) * 2000-05-24 2002-03-07 Litech L L C Cellule electrochimique et accumulateur aux ions de lithium
US6436576B1 (en) 2000-05-24 2002-08-20 Litech, L.L.C. Carbon-carbon composite as an anode for lithium secondary non-aqueous electrochemical cells
US6489061B1 (en) 2000-05-24 2002-12-03 Litech, L.L.C. Secondary non-aquenous electrochemical cell configured to improve overcharge and overdischarge acceptance ability
US6949314B1 (en) 2002-08-19 2005-09-27 Litech, L.L.C. Carbon-carbon composite anode for secondary non-aqueous electrochemical cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990013924A2 (fr) * 1989-05-11 1990-11-15 Moli Energy Limited Electrodes carbonees pour element accumulateur au lithium
EP0627776A2 (fr) * 1993-05-14 1994-12-07 Sharp Kabushiki Kaisha Batterie secondaire au lithium
WO1996041394A1 (fr) * 1995-06-07 1996-12-19 Duracell Inc. Procede d'amelioration de cellule a ion lithium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990013924A2 (fr) * 1989-05-11 1990-11-15 Moli Energy Limited Electrodes carbonees pour element accumulateur au lithium
EP0627776A2 (fr) * 1993-05-14 1994-12-07 Sharp Kabushiki Kaisha Batterie secondaire au lithium
WO1996041394A1 (fr) * 1995-06-07 1996-12-19 Duracell Inc. Procede d'amelioration de cellule a ion lithium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001091208A3 (fr) * 2000-05-24 2002-03-07 Litech L L C Cellule electrochimique et accumulateur aux ions de lithium
US6436576B1 (en) 2000-05-24 2002-08-20 Litech, L.L.C. Carbon-carbon composite as an anode for lithium secondary non-aqueous electrochemical cells
US6489061B1 (en) 2000-05-24 2002-12-03 Litech, L.L.C. Secondary non-aquenous electrochemical cell configured to improve overcharge and overdischarge acceptance ability
US6949314B1 (en) 2002-08-19 2005-09-27 Litech, L.L.C. Carbon-carbon composite anode for secondary non-aqueous electrochemical cells

Also Published As

Publication number Publication date
ZA983067B (en) 1998-10-13
AU6966598A (en) 1998-11-11

Similar Documents

Publication Publication Date Title
EP0249331B1 (fr) Methode de fabrication d'une batterie secondaire
US5750282A (en) Process for improving lithium ion cell
US6027833A (en) Nonaqueous electrolyte secondary cell
CN101515640B (zh) 一种负极和包括该负极的锂离子二次电池
KR19980080096A (ko) 리튬 2차 전지 및 음극 제조방법
JP3774315B2 (ja) 非水電解質二次電池
JPH103920A (ja) リチウム二次電池及びその製造方法
Yamaura et al. High voltage, rechargeable lithium batteries using newly-developed carbon for negative electrode material
KR19980064693A (ko) 비수성 전해액 2차 전지
US5522127A (en) Method of manufacturing a non-aqueous electrolyte secondary cell
JP4053630B2 (ja) 非水電解質二次電池
JP3236400B2 (ja) 非水二次電池
JPH09245830A (ja) 非水電解液二次電池
JP3444616B2 (ja) 非水二次電池用負極
WO1998047195A1 (fr) Technique permettant d'ameliorer une pile au lithium
JP3475530B2 (ja) 非水電解質二次電池
JP2000195550A (ja) 非水電解液二次電池
JP4717275B2 (ja) 非水系二次電池
JP4080110B2 (ja) 非水電解質電池
JP2007122975A (ja) 非水電解質二次電池
JP3568247B2 (ja) 非水電解液二次電池
JPH06150970A (ja) 二次電池
CN118076558B (zh) 难石墨化碳、混合碳粉、锂离子二次电池用负极、锂离子二次电池
JP3104264B2 (ja) コイン型非水電解液二次電池
JP2001006671A (ja) リチウム二次電池のエージング処理方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998544121

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase