WO2011162176A1 - Matériau actif pour électrode, son procédé de fabrication, et batterie auxiliaire à électrolyte non aqueux contenant ce matériau - Google Patents

Matériau actif pour électrode, son procédé de fabrication, et batterie auxiliaire à électrolyte non aqueux contenant ce matériau Download PDF

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Publication number
WO2011162176A1
WO2011162176A1 PCT/JP2011/063905 JP2011063905W WO2011162176A1 WO 2011162176 A1 WO2011162176 A1 WO 2011162176A1 JP 2011063905 W JP2011063905 W JP 2011063905W WO 2011162176 A1 WO2011162176 A1 WO 2011162176A1
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Prior art keywords
active material
electrode active
lithium
barium
compound
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PCT/JP2011/063905
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English (en)
Japanese (ja)
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徹 川合
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株式会社 村田製作所
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Priority to JP2012521451A priority Critical patent/JPWO2011162176A1/ja
Publication of WO2011162176A1 publication Critical patent/WO2011162176A1/fr

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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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 generally relates to an electrode active material, a method for producing the same, and a non-aqueous electrolyte secondary battery including the electrode active material, and more specifically, an electrode active material comprising a lithium titanium composite oxide having a spinel structure and the same
  • the present invention relates to a manufacturing method and a nonaqueous electrolyte secondary battery including the same.
  • secondary batteries with high energy density and long life are expected as cordless power sources for these electronic devices.
  • secondary batteries have been developed that use an alkali metal ion such as lithium ion as a charge carrier and use an electrochemical reaction associated with charge exchange.
  • lithium ion secondary batteries having a large energy density are widely used.
  • a lithium-containing transition metal oxide such as lithium cobaltate or lithium manganate is used as the positive electrode active material.
  • a carbon material capable of inserting and extracting lithium ions is used as the negative electrode active material.
  • graphite such as natural graphite and artificial graphite has a discharge voltage as low as 0.2 V with respect to lithium metal, and when graphite is used as a negative electrode active material, a battery having a discharge voltage of 3.6 V is possible.
  • a carbon material is used for the negative electrode, if a short circuit occurs inside the battery, lithium ions may flow from the negative electrode to the positive electrode at once, and the temperature may increase rapidly.
  • Lithium titanium composite oxide is a material that can occlude and release lithium ions without changing the structure and size of the crystal lattice, and is a promising electrode active material for highly reliable nonaqueous electrolyte secondary batteries.
  • Patent Document 1 in International Publication No. 2006/106700 (hereinafter referred to as Patent Document 1), in order to obtain a lithium ion battery excellent in high rate charge / discharge characteristics, a composition formula in which a part of the lithium titanate element is substituted with Al : Li [Li (1-x) / 3 Al x Ti (5-2x) / 3 ] O 4 (0 ⁇ x ⁇ 1) is proposed as an electrode active material for a lithium ion battery.
  • a lithium ion battery used as a negative electrode active material is disclosed.
  • an object of the present invention is to provide an electrode active material containing a spinel type lithium titanate as a main component and capable of improving the charge capacity at least during rapid charging of a nonaqueous electrolyte secondary battery, and a method for producing the same, And a nonaqueous electrolyte secondary battery including the same.
  • the present inventor has mixed a barium compound into at least a lithium compound and a titanium compound as starting materials, and baked to mainly produce lithium titanate having a spinel structure.
  • a barium compound into at least a lithium compound and a titanium compound as starting materials, and baked to mainly produce lithium titanate having a spinel structure.
  • the electrode active material according to the present invention contains lithium titanate having a spinel structure and a barium compound, and barium is contained in a molar ratio exceeding 0 mol part and less than 5 mol parts with respect to 100 mol parts of lithium.
  • An electrode active material according to the present invention includes lithium titanate having a spinel structure and a barium compound, and barium is contained in a molar ratio of 0.025 mol part or more and 4.6 mol part or less with respect to 100 mol parts of lithium. It is preferable that
  • the method for producing an electrode active material according to the present invention includes at least a mixing step of mixing a lithium compound, a titanium compound, and a barium compound to obtain a mixture, and a baking step of baking the mixture.
  • the mixing step it is preferable to mix the lithium compound, the titanium compound, and the barium compound so that barium is contained in a molar ratio exceeding 0 mol part and less than 5 mol parts with respect to 100 mol parts of lithium.
  • the lithium compound, the titanium compound, and the barium compound are mixed so that barium is contained in a molar ratio of 0.025 mol part or more and 4.6 mol part or less with respect to 100 mol parts of lithium. It is preferable.
  • the barium compound mixed in the mixing step is barium carbonate.
  • the lithium compound is preferably lithium carbonate.
  • the titanium compound is preferably titanium oxide.
  • the non-aqueous electrolyte secondary battery of the present invention uses the above electrode active material as an electrode material.
  • the non-aqueous electrolyte secondary battery of the present invention uses an electrode active material produced by the above production method as an electrode material.
  • an electrode active material containing spinel type lithium titanate as a main component an electrode active material capable of improving the charge capacity at least during rapid charging of a nonaqueous electrolyte secondary battery is obtained. Can do.
  • the electrode active material of the present invention includes a spinel type lithium titanate and a barium compound, and barium is contained in a molar ratio exceeding 0 mol part and less than 5 mol parts with respect to 100 mol parts of lithium. Yes.
  • the electrode active material of the present invention includes lithium titanate having a spinel structure and a barium compound, and barium is 0.025 mol part or more and 4.6 mol part or less with respect to 100 mol parts of lithium as a molar ratio. included.
  • the electrode active material of the present invention is an electrode active material containing spinel type lithium titanate as a main component by containing a barium compound separately from lithium titanate and containing barium in the above molar ratio. It is possible to improve the charging capacity per unit weight of the electrode active material at least during rapid charging, and an electrode active material having excellent rapid charging characteristics can be obtained.
  • the electrode active material When barium is contained in the electrode active material in a molar ratio of more than 0 mole part and less than 5 mole parts with respect to 100 mole parts of lithium, an electrode active material having at least good quick charge characteristics can be obtained. Moreover, when barium is contained in a molar ratio of 0.025 mol part or more and 4.6 mol part or less with respect to 100 mol parts of lithium, an electrode active material having at least quick charge characteristics can be obtained. Further, the electrode active material preferably contains barium in a molar ratio of 0.025 mol part or more and 3.7 mol part or less with respect to 100 mol parts of lithium. In this case, it is possible to obtain an electrode active material having at least faster charging characteristics.
  • the electrode active material contains barium in a molar ratio of 0.025 mol part or more and 2.5 mol part or less with respect to 100 mol parts of lithium. In this case, an electrode active material having good rapid charge / discharge characteristics can be obtained. Furthermore, it is preferable that the electrode active material contains barium in a molar ratio of 0.125 mol part or more and 2.5 mol part or less with respect to 100 mol parts of lithium. In this case, an electrode active material with better rapid charge / discharge characteristics can be obtained.
  • examples of the spinel-type lithium titanate contained in the electrode active material of the present invention include Li 4 Ti 5 O 12 .
  • Lithium titanate may contain elements other than lithium, titanium, and oxygen.
  • the barium compound present separately from lithium titanate may be a compound that acts as an electrode active material or a compound that does not act as an electrode active material.
  • a part of barium may be contained as a compound substituted in spinel type lithium titanate.
  • the method for producing an electrode active material of the present invention includes at least a mixing step of mixing a lithium compound, a titanium compound, and a barium compound to obtain a mixture, and a baking step of baking the mixture.
  • the mixing step it is preferable to mix the lithium compound, the titanium compound, and the barium compound so that barium is contained in a molar ratio exceeding 0 mol part and less than 5 mol parts with respect to 100 mol parts of lithium. More preferably, the lithium compound, the titanium compound, and the barium compound are mixed so that barium is contained in a molar ratio of 0.025 mol part or more and 4.6 mol part or less with respect to 100 mol parts of lithium.
  • the barium compound is preferably barium carbonate.
  • the lithium compound is preferably lithium carbonate.
  • the titanium compound is preferably titanium oxide.
  • examples of the lithium compound include lithium oxides, carbonates, inorganic acid salts, organic acid salts, chlorides, and the like. Lithium etc. are mentioned. In particular, it is preferable to use lithium carbonate as the lithium compound.
  • examples of the titanium compound include titanium oxides, carbonates, inorganic acid salts, organic acid salts, and chlorides.
  • titanium oxide it is preferable to use titanium oxide as the titanium compound.
  • examples of the barium compound include barium oxides, carbonates, inorganic acid salts, organic acid salts, and chlorides. Specific examples include barium carbonate and barium oxide. In particular, it is preferable to use barium carbonate as the barium compound.
  • the mixing method, mixing conditions in the mixing step, and the baking method and baking conditions in the baking step can be arbitrarily set in consideration of the required characteristics, productivity, and the like of the nonaqueous electrolyte secondary battery.
  • a negative electrode is formed.
  • a negative electrode active material is mixed with a conductive agent and a binder, an organic solvent or water is added to form a negative electrode active material slurry, and this negative electrode active material slurry is coated on the electrode current collector by an arbitrary coating method.
  • the negative electrode is formed by drying.
  • a positive electrode is formed.
  • a positive electrode active material is mixed with a conductive agent and a binder, an organic solvent or water is added to form a positive electrode active material slurry, and this positive electrode active material slurry is coated on the electrode current collector by an arbitrary coating method.
  • the positive electrode is formed by drying.
  • the positive electrode active material is not particularly limited, and a lithium transition metal composite containing lithium compounds such as lithium cobaltate, lithium manganate, and lithium nickelate, and optionally aluminum in addition to manganese and nickel.
  • a lithium transition metal composite containing lithium compounds such as lithium cobaltate, lithium manganate, and lithium nickelate, and optionally aluminum in addition to manganese and nickel.
  • An oxide or the like can be used.
  • the binder is not particularly limited, and various resins such as polyethylene, polyvinylidene fluoride, polyhexafluoropropylene, polytetrafluoroethylene, polyethylene oxide, and carboxymethylcellulose can be used.
  • the organic solvent is not particularly limited, and examples thereof include basic solvents such as dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, propylene carbonate, diethyl carbonate, dimethyl carbonate, and ⁇ -butyrolactone, acetonitrile, tetrahydrofuran, Nonaqueous solvents such as nitrobenzene and acetone, and protic solvents such as methanol and ethanol can be used.
  • the kind of organic solvent, the compounding ratio of the organic compound and the organic solvent, the kind of additive and the amount of the additive, and the like can be arbitrarily set in consideration of the required characteristics and productivity of the secondary battery.
  • the positive electrode 14 obtained above is impregnated into the electrolyte, so that the positive electrode 14 is infiltrated with the electrolyte, and then the positive electrode current collector at the center of the bottom of the case 11 that also serves as the positive electrode terminal.
  • the positive electrode 14 is placed on the top.
  • the separator 16 impregnated with the electrolyte is laminated on the positive electrode 14, the negative electrode 15 and the current collector plate 17 are sequentially laminated, and the electrolyte is injected into the internal space.
  • a metal spring member 18 is placed on the current collector plate 17, and a gasket 13 is arranged on the periphery, and a sealing plate 12 that also serves as a negative electrode terminal is fixed to the case 11 with a caulking machine or the like to seal the exterior.
  • a sealing plate 12 that also serves as a negative electrode terminal is fixed to the case 11 with a caulking machine or the like to seal the exterior.
  • the electrolyte is interposed between the positive electrode 14 and the negative electrode 15 which is a counter electrode, and transports charge carriers between the two electrodes.
  • an electrolyte one having an ionic conductivity of 10 ⁇ 5 to 10 ⁇ 1 S / cm at room temperature can be used.
  • an electrolytic solution in which an electrolyte salt is dissolved in an organic solvent can be used.
  • the electrolyte salt include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5 SO 2 ) 3 C, or the like can be used.
  • organic solvent ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, etc. are used. be able to.
  • a solid electrolyte for electrolyte.
  • the polymer compound used in the solid electrolyte include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, and fluoride.
  • Vinylidene fluoride polymers such as vinylidene-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and acrylonitrile-methyl methacrylate copolymer Polymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-a Examples include acrylonitrile-based polymers such as lauric acid copolymers and acrylonitrile-vinyl acetate copolymers, as well as polyethylene oxide, ethylene oxide-propylene oxide copolymers, and polymers of these acrylates and methacrylates.
  • electrolyte solution contains electrolyte solution and made it gelatinous as electrolyte.
  • a polymer compound containing an electrolyte salt may be used as an electrolyte as it is.
  • an electrolyte Li 2 S-P 2 S 5 based, Li 2 S-B 2 S 3 type, may be used an inorganic solid electrolyte such as sulfide glass represented by Li 2 S-SiS 2 system.
  • the coin-type secondary battery has been described, but it is needless to say that the battery shape is not particularly limited, and can be applied to a cylindrical type, a square type, a sheet type, and the like. Further, the exterior method is not particularly limited, and a metal case, a mold resin, an aluminum laminate film, or the like may be used.
  • the electrode active material of the present invention is used for the negative electrode, but it can also be applied to the positive electrode.
  • the electrode active material is used for a non-aqueous electrolyte secondary battery has been described, but it can also be used for a primary battery.
  • Example shown below is an example and this invention is not limited to the following Example.
  • Examples 1 to 7 and Comparative Examples 1 to 3 of a coin-type nonaqueous electrolyte secondary battery using an electrode active material containing spinel type lithium titanate as a main component and using the electrode active material will be described.
  • An electrode active material composed mainly of lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure was synthesized by the following method.
  • the raw materials lithium carbonate (Li 2 CO 3 ), titanium oxide (TiO 2 ), and barium carbonate (BaCO 3 ) have the following molar ratios of lithium (Li), titanium (Ti), and barium (Ba):
  • a slurry is obtained by weighing so as to have the ratio shown in Examples 1 to 7 and Comparative Examples 1 to 3 and mixing in a wet manner using water as a solvent by a ball mill using alumina balls having a diameter of 5 mm. It was. After the slurry thus obtained was spray-dried, the dried powder was fired in the atmosphere at a temperature of 850 ° C. for 1 hour to prepare each electrode active material.
  • the electrode active material contains lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: (0.025 mol part (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material includes lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: 0.125 mol part (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material contains lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: 0.25 mol part (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material includes lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: 1.25 mol part (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material includes lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: (2.5 mol part (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material contains lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: (The amount is 3.7 mol parts (Ba addition amount) with respect to 100 mol parts.)
  • the electrode active material includes lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: 4.6 mol parts (added amount of Ba) is included with respect to 100 mol parts.)
  • the electrode active material includes only spinel type lithium titanate (Li 4 Ti 5 O 12 ), and Ba is not included.)
  • the electrode active material contains lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: (5 mol parts (Ba addition amount) is included with respect to 100 mol parts.)
  • the electrode active material includes lithium titanate (Li 4 Ti 5 O 12 ) having a spinel structure and a barium compound, and Ba is Li: 10 mol parts (Ba addition amount) is included with respect to 100 mol parts.)
  • a coin-type non-aqueous electrolyte secondary battery as shown in FIG. 1 was produced using the obtained electrode active materials.
  • a coin-type nonaqueous electrolyte secondary battery 1 includes a case 11 that also serves as a positive electrode terminal, a sealing plate 12 that also serves as a negative electrode terminal, and a gasket 13 that insulates the case 11 and the sealing plate 12.
  • a positive electrode 14 of the coin-type nonaqueous electrolyte secondary battery 1 shown in FIG. 1 is produced using each of the electrode active materials produced above, and the nonaqueous materials of Examples 1 to 7 and Comparative Examples 1 to 3 are produced. The effect as an electrode active material for electrolyte secondary batteries was verified.
  • the electrode active material prepared above, acetylene black, and polyvinylidene fluoride were weighed so as to have a mass ratio of 88: 6: 6 and mixed to prepare an electrode mixture.
  • This electrode mixture was dispersed in a solvent (N-methyl-2-pyrrolidone) to prepare an electrode slurry.
  • This electrode slurry was applied on the surface of an aluminum foil having a thickness of 20 ⁇ m at a coating amount of 6 mg / cm 2 , dried at a temperature of 140 ° C., pressed at a pressure of 1 ton / cm 2 , and then circular with a diameter of 12 mm.
  • An electrode sheet was produced by punching into a plate.
  • This electrode sheet was used as the positive electrode 14 of the coin-type nonaqueous electrolyte secondary battery 1 shown in FIG.
  • the negative electrode 15 a disk made of a metal lithium foil having a diameter of 15.5 mm was used.
  • the negative electrode 15 and the current collector plate 17 were bonded together.
  • the separator 16 a disk-like polyethylene porous film having a diameter of 16 mm was used.
  • the electrolytic solution a solution in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 3: 7 and lithium hexafluorophosphate (LiPF 6 ) was mixed so as to be 1 mol was used. In this way, a coin-type non-aqueous electrolyte secondary battery 1 having a diameter of 20 mm and a thickness of 3.2 mm was produced.
  • the charge / discharge characteristics were evaluated using the coin-type non-aqueous electrolyte secondary battery 1 produced as described above. After charging and discharging for 3 cycles in a constant temperature bath at 25 ° C. with a current value of 0.2 C and a voltage range of 1.0 to 3.0 V, assuming that the current value at which charging or discharging ends in 1 hour is 1 C. The battery was discharged at a constant voltage of 3.0 V for 2 hours and then charged to 1.0 V at a current value of 10 C, and the charge capacity (10 C charge capacity) at a current value of 10 C was measured.
  • the electrode active material of the present invention contains a spinel type lithium titanate as a main component, and is an electrode active material capable of improving the charge capacity at least during rapid charging of a nonaqueous electrolyte secondary battery. It is useful for manufacturing a water electrolyte secondary battery.

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Cette invention concerne un matériau actif pour électrode qui permet d'augmenter rapidement la capacité de décharge pendant la décharge rapide d'une batterie auxiliaire à électrolyte non aqueux et qui contient du titanate de lithium à structure en spinelle comme composant principal. L'invention concerne également un procédé de fabrication de ce matériau et une batterie auxiliaire à électrolyte non aqueux comprenant ledit matériau. Le matériau actif pour électrode contient du titanate de lithium à structure spinelle et un composé de baryum, le rapport molaire du baryum étant de plus de plus de 0 mole à moins de 5 moles par 100 moles de lithium.
PCT/JP2011/063905 2010-06-22 2011-06-17 Matériau actif pour électrode, son procédé de fabrication, et batterie auxiliaire à électrolyte non aqueux contenant ce matériau WO2011162176A1 (fr)

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JP2012521451A JPWO2011162176A1 (ja) 2010-06-22 2011-06-17 電極活物質およびその製造方法、ならびにそれを備えた非水電解質二次電池

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JP2010-141267 2010-06-22
JP2010141267 2010-06-22

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07169456A (ja) * 1993-03-25 1995-07-04 Ngk Insulators Ltd リチウムイオン伝導体及びリチウム電池のカソード材料
JP2001126728A (ja) * 1999-10-26 2001-05-11 Toyota Motor Corp リチウムイオン２次電池用負極
JP2009245929A (ja) * 2008-03-13 2009-10-22 Toshiba Corp 電池用活物質、非水電解質電池および電池パック

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07169456A (ja) * 1993-03-25 1995-07-04 Ngk Insulators Ltd リチウムイオン伝導体及びリチウム電池のカソード材料
JP2001126728A (ja) * 1999-10-26 2001-05-11 Toyota Motor Corp リチウムイオン２次電池用負極
JP2009245929A (ja) * 2008-03-13 2009-10-22 Toshiba Corp 電池用活物質、非水電解質電池および電池パック

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