WO2012086618A1 - Matériau actif d'électrode négative, électrode négative et batterie secondaire à électrolyte non aqueux - Google Patents

Matériau actif d'électrode négative, électrode négative et batterie secondaire à électrolyte non aqueux Download PDF

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WO2012086618A1
WO2012086618A1 PCT/JP2011/079435 JP2011079435W WO2012086618A1 WO 2012086618 A1 WO2012086618 A1 WO 2012086618A1 JP 2011079435 W JP2011079435 W JP 2011079435W WO 2012086618 A1 WO2012086618 A1 WO 2012086618A1
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negative electrode
active material
secondary battery
electrolyte secondary
electrode active
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PCT/JP2011/079435
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English (en)
Japanese (ja)
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英高 柴田
大塚　正博
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株式会社 村田製作所
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 a negative electrode active material, a negative electrode, and a non-aqueous electrolyte secondary battery, and more specifically, a negative electrode active material including a carbon material, a negative electrode including the negative electrode active material, and a non-electrode including the negative electrode
  • the present invention relates to a water electrolyte secondary battery.
  • 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.
  • Patent Document 1 JP 2001-57230 A (hereinafter referred to as Patent Document 1) describes using graphite, soft carbon, or hard carbon as the negative electrode active material.
  • active research has been conducted on materials for negative electrode active materials.
  • an object of the present invention is to provide a negative electrode active material capable of improving the output characteristics of the battery, a negative electrode including the negative electrode active material, and a nonaqueous electrolyte secondary battery including the negative electrode.
  • the negative electrode active material according to the present invention includes graphite and surface-amorphized soft carbon.
  • the negative electrode active material of the present invention preferably contains graphite and surface amorphized soft carbon in a mass ratio of 95: 5 to 30:70.
  • the graphite contains surface-amorphized graphite.
  • the negative electrode according to the present invention includes a negative electrode active material having the characteristics described above.
  • the filling density of the negative electrode mixture is preferably 1.2 g / cm 3 or more and 1.5 g / cm 3 or less.
  • a non-aqueous electrolyte secondary battery according to the present invention includes the above negative electrode.
  • the output DCR of the battery can be reduced, so that the output characteristics of the battery can be improved.
  • the present inventor has repeatedly studied using various carbon materials as the negative electrode active material. As a result, it has been found that when the negative electrode active material contains graphite and surface amorphized soft carbon, the output DCR of the battery can be reduced.
  • the present invention has been made based on such knowledge of the present inventor.
  • the particles of the surface-amorphized soft carbon are an inner layer made of amorphous soft carbon and a surface formed on the surface of the inner layer and made more amorphous than the soft carbon of the inner layer. Composed of layers.
  • the surface-amorphized soft carbon particles having such a structure are formed, for example, by coating the surface of the soft carbon particles that become an amorphous inner layer with amorphous carbon from the inner layer.
  • the negative electrode active material contains graphite and surface-amorphized soft carbon, so that the non-aqueous electrolyte secondary battery including the negative electrode containing the negative electrode active material reduces the output DCR of the battery. And the output characteristics of the battery can be improved.
  • the negative electrode active material contains graphite and surface amorphized soft carbon in a mass ratio of 95: 5 to 30:70
  • the output DCR of the battery can be more effectively reduced, and the output characteristics of the battery can be reduced. Can be further improved.
  • the mass ratio of soft carbon is larger than 70%, the output DCR of the battery increases.
  • capacitance as a battery becomes small by the fall of a negative electrode capacity
  • the output DCR of the battery can be further reduced, and the output characteristics of the battery can be further improved.
  • the positive electrode and the negative electrode of the non-aqueous electrolyte secondary battery are alternately stacked via a separator.
  • the structure of the battery element may be composed of a stack of a plurality of strip-shaped positive electrodes, a plurality of strip-shaped separators and a plurality of strip-shaped negative electrodes, a stack of so-called single-wafer structures. It may be configured by folding and interposing a strip-shaped positive electrode and a strip-shaped negative electrode alternately.
  • a winding type structure in which a long positive electrode, a long separator, and a long negative electrode are wound may be employed. In the following examples, a single-wafer laminated body is adopted as the battery element structure.
  • a positive electrode mixture layer including a positive electrode active material, a conductive agent, and a binder is formed on both surfaces of the positive electrode current collector.
  • the positive electrode current collector is made of aluminum or copper.
  • the positive electrode active material is lithium cobalt oxide composite oxide, lithium manganate composite oxide, lithium nickelate composite oxide, lithium-nickel-manganese-cobalt composite oxide, lithium-manganese-nickel composite oxide, lithium-manganese- A cobalt composite oxide, a lithium-nickel-cobalt composite oxide, or the like can be used. Further, the positive electrode active material may be a mixture of the above materials.
  • the positive electrode active material may be a lithium-containing phosphate compound having an olivine type structure such as lithium iron phosphate represented by LiFePO 4 . If it has an olivine type structure, in the lithium iron phosphate represented by LiFePO 4 , a part of Fe is replaced with Al, Ti, V, Cr, Mn, Co, Ni, Zr, Nb, etc. Also good. A part of P may be replaced with B, Si, or the like. A carbon material such as acetylene black is used as the conductive agent for the positive electrode. Polyvinylidene fluoride (PVDF) or polyamideimide (PAI) is used as the binder for binding the positive electrode active material and the conductive agent.
  • PVDF polyvinylidene fluoride
  • PAI polyamideimide
  • a negative electrode mixture layer containing the negative electrode active material (graphite and surface-amorphized soft carbon) and a binder is formed on both surfaces of the negative electrode current collector.
  • the negative electrode current collector is made of copper.
  • the binder for binding the negative electrode active material polyvinylidene fluoride, polyacrylonitrile or polyamideimide is used, or a mixture of a latex binder such as styrene butadiene rubber and a thickener such as carboxymethyl cellulose is used. .
  • the filling density of the negative electrode mixture in the negative electrode is preferably 1.2 g / cm 3 or more and 1.5 g / cm 3 or less.
  • the filling density of the negative electrode mixture is within the above range, the capacity retention rate of the battery can be increased, and the AC resistance increase rate can be decreased.
  • the nonaqueous electrolytic solution is prepared by dissolving the supporting electrolyte in a nonaqueous solvent.
  • a solution obtained by dissolving LiPF 6 at a concentration of 1.0 mol / L in a non-aqueous solvent is used.
  • supporting electrolytes other than LiPF 6 include lithium salts such as LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , and LiSiF 6. Can be mentioned.
  • LiPF 6 and LiBF 4 are particularly preferably used as the supporting electrolyte from the viewpoint of oxidation stability.
  • a supporting electrolyte is preferably used by being dissolved in a nonaqueous solvent at a concentration of 0.1 mol / L to 3.0 mol / L, and at a concentration of 0.5 mol / L to 2.0 mol / L. More preferably, it is used after being dissolved.
  • the non-aqueous solvent include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), which are low viscosity solvents. And a lower chain carbonate of the above are used.
  • the separator is not particularly limited, and a conventionally known separator can be used.
  • the separator is not limited by its name, and a solid electrolyte or gel electrolyte having a function (role) as a separator may be used instead of the separator.
  • a separator containing an inorganic material such as alumina or zirconia may be used.
  • the separator uses a porous film containing polypropylene and / or polyethylene.
  • Example shown below is an example and this invention is not limited to the following Example.
  • the configurations of the negative electrode active materials were varied to prepare the non-aqueous electrolyte secondary batteries of Examples and Comparative Examples.
  • Example 1 (Preparation of negative electrode) A negative electrode active material comprising a mixture of surface amorphized graphite (hereinafter referred to as surface amorphized GC) and surface amorphized soft carbon (hereinafter referred to as surface amorphized SC), and a binder Polyvinylidene fluoride was blended at a mass ratio of 95: 5 and kneaded with N-methyl-2-pyrrolidone to prepare a negative electrode mixture slurry. At this time, the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 80:20 to prepare a negative electrode active material.
  • surface amorphized GC surface amorphized graphite
  • SC surface amorphized soft carbon
  • non-aqueous electrolyte As non-aqueous solvent, ethylene carbonate is a cyclic carbonate, diethyl carbonate a chain carbonate 3: with 7 mixed solvent were mixed at a volume ratio of the LiPF 6 as a supporting electrolyte 1 mol / L in the mixed solvent It was made to melt
  • lead tabs 14 and 15 were provided on the positive electrode 11 and the negative electrode 12 produced as described above.
  • the positive electrode 11 and the negative electrode 12 were laminated with a separator 13 made of a polypropylene microporous membrane permeable to lithium ions.
  • the battery element 10 was produced.
  • Sealants 16 and 17 were attached to the lead tabs 14 and 15, and as shown in FIG. 2, the laminate was housed in an outer packaging material 20 made of a laminate film containing aluminum as an intermediate layer. Then, after pouring the non-aqueous electrolyte produced above into the outer packaging material 20, the non-aqueous electrolyte secondary battery 1 was produced by sealing the opening of the outer packaging material 20.
  • the obtained nonaqueous electrolyte secondary battery 1 was charged at a constant current up to a voltage of 0.2 V at a current value of 6 mA, and then charged at a constant voltage until the current value became 0.6 mA at a voltage value of 0.2 V. .
  • the non-aqueous electrolyte secondary battery 1 charged in this way is plotted with respect to the current value after plotting the voltage value after 10 seconds of pulse discharge at each current value of 6 to 160 mA. A straight line was obtained, and the slope was calculated as the output DCR.
  • a decrease in potential due to insertion of lithium into the negative electrode active material constituting the negative electrode 12 is defined as charging, and a rise in potential due to lithium desorption from the negative electrode active material is defined as discharge.
  • Example 1 As a negative electrode active material, a mixture of a surface-amorphized GC and a soft carbon whose surface is not amorphized (hereinafter referred to as SC without surface modification) is used. A nonaqueous electrolyte secondary battery 1 was produced in the same manner as in Example 1 except that SC was mixed at a mass ratio of 80:20 to produce a negative electrode active material. With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 2 (Comparative Example 2) Using a mixture of surface amorphized GC and hard carbon (hereinafter referred to as HC) as a negative electrode active material, the surface amorphized GC and HC are mixed at a mass ratio of 80:20 to obtain a negative electrode active material.
  • a nonaqueous electrolyte secondary battery 1 was produced in the same manner as in Example 1 except that it was produced. With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 3 Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 100: 0, that is, the negative electrode active material was produced using only the surface amorphized GC.
  • a nonaqueous electrolyte secondary battery 1 was produced in the same manner as described above. In order to make the battery capacity the same as that of the nonaqueous electrolyte secondary battery 1 produced in Example 1, the basis weight of the negative electrode mixture per unit area was 5.0 mg / cm 2 and the packing density was 1.40 g. / Cm 3 . With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 2 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 98: 2 to prepare a negative electrode active material. Produced. In order to make the battery capacity the same as that of the non-aqueous electrolyte secondary battery 1 produced in Example 1, the basis weight of the negative electrode mixture per unit area was 5.0 mg / cm 2 and the packing density was 1.40 g. / Cm 3 . With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 3 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 97: 3 to prepare a negative electrode active material. Produced.
  • the basis weight of the negative electrode mixture per unit area was 5.0 mg / cm 2 and the packing density was 1.40 g. / Cm 3 .
  • the output DCR was calculated in the same manner as in Example 1.
  • Example 4 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 95: 5 to prepare a negative electrode active material. Produced. In order to make the battery capacity the same as that of the non-aqueous electrolyte secondary battery 1 produced in Example 1, the basis weight of the negative electrode mixture per unit area was 5.0 mg / cm 2 and the packing density was 1.40 g. / Cm 3 . With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 5 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 90:10 to prepare a negative electrode active material. Produced. In order to make the battery capacity the same as that of the non-aqueous electrolyte secondary battery 1 produced in Example 1, the basis weight of the negative electrode mixture per unit area was 5.2 mg / cm 2 and the packing density was 1.40 g. / Cm 3 . With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 6 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 60:40 to produce a negative electrode active material. Produced.
  • the basis weight of the negative electrode mixture per unit area was 5.9 mg / cm 2 and the packing density was 1.30 g. / Cm 3 .
  • the output DCR was calculated in the same manner as in Example 1.
  • Example 7 The non-aqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 50:50 to prepare a negative electrode active material. Produced. In order to make the battery capacity the same as that of the non-aqueous electrolyte secondary battery 1 produced in Example 1, the basis weight of the negative electrode mixture per unit area was 6.1 mg / cm 2 and the packing density was 1.30 g. / Cm 3 . With respect to the obtained nonaqueous electrolyte secondary battery 1, the output DCR was calculated in the same manner as in Example 1.
  • Example 8 The nonaqueous electrolyte secondary battery 1 was manufactured in the same manner as in Example 1 except that the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 30:70 to produce a negative electrode active material. Produced.
  • the basis weight of the negative electrode mixture per unit area was 6.7 mg / cm 2 and the packing density was 1.20 g. / Cm 3 .
  • the output DCR was calculated in the same manner as in Example 1.
  • Table 1 shows the output DCRs of Example 1 and Comparative Examples 1 and 2 calculated as described above, and Table 2 shows the output DCRs of Comparative Example 3 and Examples 2 to 8.
  • the filling density of the negative electrode mixture was varied to produce the non-aqueous electrolyte secondary battery of the example.
  • Example 9 (Preparation of negative electrode) A negative electrode active material composed of a mixture of surface amorphized GC and surface amorphized SC and polyvinylidene fluoride as a binder were blended at a mass ratio of 95: 5, and N-methyl- A negative electrode mixture slurry was prepared by kneading with 2-pyrrolidone. At this time, the surface amorphized GC and the surface amorphized SC were mixed at a mass ratio of 85:15 to prepare a negative electrode active material. This negative electrode mixture slurry was applied onto both sides of a copper foil as a negative electrode current collector, dried, and then rolled with a rolling roller to adjust the packing density of the negative electrode mixture to produce a negative electrode. The weight per unit area of the negative electrode mixture per unit area at this time was 5.0 mg / cm 2 and the packing density was 1.0 g / cm 3 .
  • a positive electrode active material composed of lithium iron phosphate represented by LiFePO 4 , a carbon material as a conductive agent, and polyvinylidene fluoride as a binder were blended in a mass ratio of 88: 6: 6,
  • a positive electrode mixture slurry was prepared by kneading with N-methyl-2-pyrrolidone. This positive electrode mixture slurry was applied onto both surfaces of an aluminum foil as a positive electrode current collector, dried, and then rolled with a rolling roller to adjust the packing density of the positive electrode mixture to produce a positive electrode.
  • the weight per unit area of the positive electrode mixture per unit area at this time was 9.5 mg / cm 2 , and the packing density was 1.85 g / cm 3 .
  • non-aqueous electrolyte As a non-aqueous solvent, ethylene carbonate as a cyclic carbonate, ethyl methyl carbonate as a chain carbonate, and dimethyl carbonate as a chain carbonate were mixed at a volume ratio of 1: 1: 1, and vinylene carbonate was changed to 0. Using 0.5 mass% and 0.5 mass% lithium difluorobis (oxalato) phosphate added, LiPF 6 as a supporting electrolyte was dissolved in this mixed solvent to a concentration of 1 mol / L, A non-aqueous electrolyte was prepared.
  • the obtained nonaqueous electrolyte secondary battery was subjected to constant current and constant voltage charging with a current value of 60 mA and an upper limit voltage of 3.8 V and a charging time of 10 hours, and then a voltage value of 2 at a current value of 60 mA.
  • the battery was discharged at a constant current until it reached 5V. After that, from a constant current and constant voltage charge with a current value of 300 mA and an upper limit voltage of 3.8 V, a stop current value of 6.0 mA, and a constant current discharge until the voltage value becomes 2.5 V with a current value of 300 mA.
  • the stabilization cycle was repeated three times. In this way, a non-aqueous electrolyte secondary battery having a capacity of about 310 mAh was produced.
  • Example 10 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9, except that the negative electrode mixture had a packing density of 1.1 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 11 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9, except that the negative electrode mixture had a packing density of 1.2 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 12 A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 9 except that the packing density of the negative electrode mixture was 1.3 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 13 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9 except that the negative electrode mixture had a packing density of 1.4 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 14 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9 except that the negative electrode mixture had a packing density of 1.5 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 15 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9, except that the negative electrode mixture had a packing density of 1.6 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Example 16 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 9 except that the negative electrode mixture had a packing density of 1.7 g / cm 3 .
  • the capacity retention rate and the rate of change in AC resistance value before and after storage were calculated in the same manner as in Example 9.
  • Table 3 shows the capacity retention rates of Examples 9 to 16 calculated as described above and the rate of change in AC resistance value before and after storage.
  • the negative electrode containing the negative electrode active material of the present invention it is possible to provide a non-aqueous electrolyte secondary battery capable of improving the output characteristics of the battery.
  • 1 nonaqueous electrolyte secondary battery
  • 10 battery element
  • 11 positive electrode
  • 12 negative electrode
  • 13 separator
  • 20 outer packaging material

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne : un matériau actif d'électrode négative qui est apte à améliorer les caractéristiques de sortie d'une batterie ; une électrode négative qui contient le matériau actif d'électrode négative ; et une batterie secondaire à électrolyte non aqueux qui comporte l'électrode négative. Un élément de batterie (10) d'une batterie secondaire à électrolyte non aqueux comporte une électrode positive (11) qui contient un matériau actif d'électrode positive et une électrode négative (12) qui contient un matériau actif d'électrode négative. Le matériau actif d'électrode négative contient du graphite et du carbone doux dont la surface est rendue amorphe.
PCT/JP2011/079435 2010-12-24 2011-12-20 Matériau actif d'électrode négative, électrode négative et batterie secondaire à électrolyte non aqueux WO2012086618A1 (fr)

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JP2010287609 2010-12-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015064974A (ja) * 2013-09-24 2015-04-09 株式会社Ｇｓユアサ 非水電解質二次電池
US11024470B2 (en) 2017-03-23 2021-06-01 Gs Yuasa International Ltd. Nonaqueous electrolyte energy storage device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11310405A (ja) * 1995-11-14 1999-11-09 Osaka Gas Co Ltd リチウム二次電池用負極材料
JP2005004974A (ja) * 2003-06-09 2005-01-06 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2009070598A (ja) * 2007-09-11 2009-04-02 Hitachi Vehicle Energy Ltd リチウム二次電池
JP2009117240A (ja) * 2007-11-08 2009-05-28 Osaka Gas Chem Kk 負極炭素材及びそれを備えたリチウム二次電池
JP2010218937A (ja) * 2009-03-18 2010-09-30 Toyota Central R&D Labs Inc リチウム二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11310405A (ja) * 1995-11-14 1999-11-09 Osaka Gas Co Ltd リチウム二次電池用負極材料
JP2005004974A (ja) * 2003-06-09 2005-01-06 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2009070598A (ja) * 2007-09-11 2009-04-02 Hitachi Vehicle Energy Ltd リチウム二次電池
JP2009117240A (ja) * 2007-11-08 2009-05-28 Osaka Gas Chem Kk 負極炭素材及びそれを備えたリチウム二次電池
JP2010218937A (ja) * 2009-03-18 2010-09-30 Toyota Central R&D Labs Inc リチウム二次電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015064974A (ja) * 2013-09-24 2015-04-09 株式会社Ｇｓユアサ 非水電解質二次電池
US11024470B2 (en) 2017-03-23 2021-06-01 Gs Yuasa International Ltd. Nonaqueous electrolyte energy storage device
US11562862B2 (en) 2017-03-23 2023-01-24 Gs Yuasa International Ltd. Nonaqueous electrolyte energy storage device

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