WO2011122261A1 - Mélange pour pile rechargeable à électrolyte non aqueux, électrode destinée à celle-ci et pile rechargeable à électrolyte non aqueux - Google Patents

Mélange pour pile rechargeable à électrolyte non aqueux, électrode destinée à celle-ci et pile rechargeable à électrolyte non aqueux Download PDF

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Publication number
WO2011122261A1
WO2011122261A1 PCT/JP2011/055337 JP2011055337W WO2011122261A1 WO 2011122261 A1 WO2011122261 A1 WO 2011122261A1 JP 2011055337 W JP2011055337 W JP 2011055337W WO 2011122261 A1 WO2011122261 A1 WO 2011122261A1
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Prior art keywords
electrolyte secondary
mixture
secondary battery
carboxyl group
polymer
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PCT/JP2011/055337
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English (en)
Japanese (ja)
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京平 萩原
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株式会社クレハ
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Priority to CN201180005985.1A priority Critical patent/CN102725889B/zh
Priority to JP2012508179A priority patent/JP5684235B2/ja
Priority to KR1020127018065A priority patent/KR101464841B1/ko
Publication of WO2011122261A1 publication Critical patent/WO2011122261A1/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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
    • 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
    • H01M4/621—Binders
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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 mixture for a nonaqueous electrolyte secondary battery, an electrode for a nonaqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries using lithium are mainly used as power sources for small electronic devices used in homes such as mobile phones, personal computers, and video camcorders as batteries that can obtain large energy with a small volume and weight. ing.
  • PVDF Polyvinylidene fluoride
  • Binder resin binder resin
  • PVDF has excellent electrochemical stability, mechanical properties, slurry properties, and the like.
  • PVDF has poor adhesion to a metal foil that is a current collector. Therefore, a method has been proposed in which a functional group such as a carboxyl group is introduced into PVDF to improve the adhesiveness to the metal foil (see, for example, Patent Documents 1 to 5).
  • PVDF tends to be unevenly distributed on the electrode surface when the amount of the binder added is small and when the electrode is manufactured by rapid drying.
  • the amount of the binder in the vicinity of the current collector is reduced, and the adhesion to the current collector is reduced.
  • the binding force between the active materials is reduced at a location where the amount of PVDF is small. Therefore, when the binder is unevenly distributed, an electrode having a low peel strength can be obtained even when PVDF having a functional group such as a carboxyl group is used.
  • an electrode using only polyacrylic acid as a binder is known (see, for example, Patent Documents 12 and 13).
  • the higher the molecular weight, the greater the adhesion, and the use of polyacrylic acid with a weight average molecular weight of 300,000 or more improves the cycle durability of the battery. It has been known.
  • the electrode becomes hard, and in the battery manufacturing process, the electrode may break when the electrode is wound, and the yield of the battery deteriorates.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and can produce a non-aqueous electrolyte secondary battery electrode and a non-aqueous electrolyte secondary battery with high productivity.
  • non-aqueous electrolyte secondary batteries that can suppress the uneven distribution of the binder in the mixture layer and has excellent peel strength between the mixture layer and the current collector when the battery electrode is manufactured
  • the purpose is to provide a mixture.
  • it aims at providing the electrode for nonaqueous electrolyte secondary batteries obtained by apply
  • the present inventors have used a specific unsaturated carboxylic acid polymer (A) and a carboxyl group-containing vinylidene fluoride polymer (B) as a binder.
  • the present invention was completed by finding that the mixture for non-aqueous electrolyte secondary batteries used in the above could solve the above problems.
  • the mixture for non-aqueous electrolyte secondary batteries of the present invention comprises at least one unsaturated carboxylic acid polymer (A) selected from polyacrylic acid and polymethacrylic acid, a carboxyl group-containing vinylidene fluoride polymer ( B), containing an electrode active material and an organic solvent, and having a weight average molecular weight in terms of polyethylene oxide measured by gel permeation chromatography (GPC) of the unsaturated carboxylic acid polymer (A) is 1,000 to 150,000.
  • GPC gel permeation chromatography
  • the weight average molecular weight in terms of polyethylene oxide measured by gel permeation chromatography (GPC) of the unsaturated carboxylic acid polymer (A) is 1,000 to 100,000.
  • the unsaturated carboxylic acid polymer (A) is 0.5 to 15% by weight per 100% by weight in total of the unsaturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B). It is preferably 0.8 to 6% by weight.
  • the specific surface area of the electrode active material is preferably 1 to 10 m 2 / g, and more preferably 2 to 6 m 2 / g.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is at least one carboxyl group-containing monomer selected from unsaturated dibasic acid, unsaturated dibasic acid monoester, acrylic acid and methacrylic acid, and vinylidene fluoride And a copolymer thereof.
  • the electrode for a non-aqueous electrolyte secondary battery of the present invention can be obtained by applying and drying the mixture for a non-aqueous electrolyte secondary battery on a current collector.
  • the nonaqueous electrolyte secondary battery electrode preferably has a mixture layer having a thickness of 20 to 150 ⁇ m formed from the nonaqueous electrolyte secondary battery mixture.
  • the non-aqueous electrolyte secondary battery of the present invention has the non-aqueous electrolyte secondary battery electrode.
  • the mixture for a non-aqueous electrolyte secondary battery of the present invention can produce a non-aqueous electrolyte secondary battery electrode and a non-aqueous electrolyte secondary battery with high productivity.
  • the uneven distribution of the binder in the mixture layer can be suppressed, and the peel strength between the mixture layer and the current collector is excellent.
  • the electrode for nonaqueous electrolyte secondary batteries and the nonaqueous electrolyte secondary battery of this invention are manufactured using this mixture for nonaqueous electrolyte secondary batteries, they are manufactured with high productivity.
  • the mixture for a non-aqueous electrolyte secondary battery of the present invention comprises at least one unsaturated carboxylic acid polymer (A) selected from polyacrylic acid and polymethacrylic acid, and a carboxyl group-containing vinylidene fluoride polymer (B).
  • a weight average molecular weight in terms of polyethylene oxide measured by gel permeation chromatography (GPC) of the unsaturated carboxylic acid polymer (A) is 1,000 to 150, 000.
  • the mixture of the present invention is usually used as a negative electrode mixture, that is, a negative electrode mixture.
  • the mixture for nonaqueous electrolyte secondary batteries of the present invention contains at least one unsaturated carboxylic acid polymer (A) selected from polyacrylic acid and polymethacrylic acid.
  • unsaturated carboxylic acid polymer (A) a polymer having a polyethylene oxide equivalent weight average molecular weight of 1,000 to 150,000 measured by gel permeation chromatography (GPC) is used.
  • the unsaturated carboxylic acid polymer (A) contained in the nonaqueous electrolyte secondary battery of the present invention may be polyacrylic acid, polymethacrylic acid, or polyacrylic acid and polymethacrylic acid. It may be a mixture.
  • the unsaturated carboxylic acid polymer (A) used in the present invention may be used alone or in combination of two or more.
  • polyacrylic acid is preferable from the viewpoint of availability.
  • polyacrylic acid examples include a homopolymer of acrylic acid and a copolymer of acrylic acid and other monomers.
  • polyacrylic acid a polymer having, in 100% by weight of the polymer, a structural unit derived from acrylic acid is usually 60% by weight or more, preferably 75% by weight or more, more preferably 90% by weight or more.
  • polyacrylic acid a homopolymer of acrylic acid is preferable.
  • a monomer that can be copolymerized with acrylic acid can be used.
  • other monomers include: methacrylic acid; ⁇ -olefins such as ethylene, propylene, and 1-butene; acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate; methyl methacrylate, ethyl methacrylate, and the like Examples thereof include alkyl methacrylates; vinyl acetate; aromatic vinyl compounds such as styrene.
  • polymethacrylic acid examples include a homopolymer of methacrylic acid and a copolymer of methacrylic acid and other monomers.
  • polymethacrylic acid a polymer having a structural unit derived from methacrylic acid in an amount of usually 60% by weight or more, preferably 75% by weight or more, more preferably 90% by weight or more in 100% by weight of the polymer is used.
  • polymethacrylic acid a homopolymer of methacrylic acid is preferable.
  • monomers capable of copolymerizing with methacrylic acid can be used.
  • the other monomers include acrylic acid; ⁇ -olefins such as ethylene, propylene, and 1-butene; acrylic acid alkyl esters such as methyl acrylate and ethyl acrylate; methyl methacrylate, ethyl methacrylate, and the like. Examples thereof include alkyl methacrylates; vinyl acetate; aromatic vinyl compounds such as styrene.
  • the unsaturated carboxylic acid polymer (A) used in the present invention preferably contains 8 ⁇ 10 ⁇ 3 to 1.4 ⁇ 10 ⁇ 2 mol / g of carboxyl groups.
  • the unsaturated carboxylic acid polymer (A) used in the present invention has a weight average molecular weight in terms of polyethylene oxide measured by gel permeation chromatography (GPC) of 1,000 to 150,000. A polymer is used.
  • the weight average molecular weight of the unsaturated carboxylic acid polymer (A) is preferably 1,000 to 100,000. When the weight average molecular weight is less than 1,000, the electrolyte solution resistance of the unsaturated carboxylic acid polymer (A) is insufficient.
  • the unsaturated carboxylic acid polymer (A) used in the present invention a part of the carboxyl group may be neutralized.
  • the mixture for nonaqueous electrolyte secondary batteries of the present invention contains a carboxyl group-containing vinylidene fluoride polymer (B) and the aforementioned unsaturated carboxylic acid polymer (A) as a binder resin (binder).
  • the carboxyl group-containing vinylidene fluoride polymer (B) is a polymer containing a carboxyl group in a polymer and obtained using at least vinylidene fluoride as a monomer.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is a polymer that is usually obtained using vinylidene fluoride and a carboxyl group-containing monomer, and other monomers may be used.
  • carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention may be used alone or in combination of two or more.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is a polymer having usually 80 parts by weight or more, preferably 85 parts by weight or more of structural units derived from vinylidene fluoride per 100 parts by weight of the polymer.
  • the carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention is usually (1) a method of copolymerizing vinylidene fluoride and a carboxyl group-containing monomer and, if necessary, another monomer (hereinafter referred to as (1) And (2) polymerizing vinylidene fluoride or copolymerizing vinylidene fluoride and other monomers, polymerizing vinylidene fluoride polymer and carboxyl group-containing monomer, or carboxyl
  • a method of grafting a carboxyl group-containing polymer onto a vinylidene fluoride polymer using a carboxyl group-containing polymer obtained by copolymerizing a group-containing monomer and another monomer hereinafter referred to as (2) (3) Polymerization of vinylidene fluoride or copolymerization of vinylidene fluoride and other monomers to produce a vinylidene fluoride polymer After the, the vinylidene fluoride-based polymer,
  • the carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention has a carboxyl group, the adhesion to the current collector is improved as compared with polyvinylidene fluoride not having a carboxyl group.
  • the carboxyl group-containing vinylidene fluoride polymer (B) has an electrolytic solution resistance equivalent to that of polyvinylidene fluoride having no carboxyl group.
  • the method (1) is used from the viewpoint of the number of steps and production cost. Is preferred. That is, the carboxyl group-containing vinylidene fluoride polymer (B) is preferably a copolymer of vinylidene fluoride and a carboxyl group-containing monomer.
  • the carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention is usually 80 to 99.9 parts by weight of vinylidene fluoride, preferably 95 to 99.7 parts by weight, and a carboxyl group-containing monomer. Usually 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight (provided that the total of vinylidene fluoride and carboxyl group-containing monomers is 100 parts by weight) copolymerized vinylidene fluoride based weight It is a coalescence.
  • the carboxyl group-containing vinylidene fluoride polymer (B) may be a polymer obtained by copolymerizing another monomer in addition to the vinylidene fluoride and the carboxyl group-containing monomer.
  • the other monomers are usually used in an amount of 0.1 to 20 parts by weight, assuming that the total of the vinylidene fluoride and carboxyl group-containing monomers is 100 parts by weight.
  • carboxyl group-containing monomer unsaturated monobasic acid, unsaturated dibasic acid, monoester of unsaturated dibasic acid and the like are preferable.
  • Examples of the unsaturated monobasic acid include acrylic acid and methacrylic acid.
  • Examples of the unsaturated dibasic acid include maleic acid and citraconic acid.
  • the unsaturated dibasic acid monoester preferably has 5 to 8 carbon atoms, and examples thereof include maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, and citraconic acid monoethyl ester. Can do.
  • the carboxyl group-containing monomer is preferably at least one monomer selected from unsaturated dibasic acid, unsaturated dibasic acid monoester, acrylic acid and methacrylic acid, maleic acid, citraconic acid, maleic acid monomethyl ester, Citraconic acid monomethyl ester, acrylic acid and methacrylic acid are more preferred.
  • the other monomer that can be copolymerized with the vinylidene fluoride and the carboxyl group-containing monomer means a monomer other than the vinylidene fluoride and the carboxyl group-containing monomer, and examples of the other monomer include a copolymer with vinylidene fluoride.
  • examples thereof include polymerizable fluorine monomers and hydrocarbon monomers such as ethylene and propylene.
  • Examples of the fluorine-based monomer copolymerizable with vinylidene fluoride include perfluoroalkyl vinyl ethers typified by vinyl fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether.
  • the said other monomer may be used individually by 1 type, and may use 2 or more types.
  • methods such as suspension polymerization, emulsion polymerization, and solution polymerization can be employed. From the viewpoint of ease of post-treatment, aqueous suspension polymerization and emulsion polymerization are preferred, and aqueous suspension is preferred. Turbid polymerization is particularly preferred.
  • all monomers used for copolymerization with suspension agents such as methylcellulose, methoxymethylcellulose, propoxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, and gelatin (Vinylidene fluoride and a carboxyl group-containing monomer, and other monomers copolymerized as necessary) 0.005 to 1.0 part by weight, preferably 0.01 to 0.4 part by weight based on 100 parts by weight Add in the range of.
  • diisopropyl peroxydicarbonate dinormalpropyl peroxydicarbonate, dinormalheptafluoropropyl peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, Di (perfluoroacyl) peroxide and the like can be used.
  • the amount used is 0.1 to 5 parts by weight, assuming that 100 parts by weight of all monomers used for copolymerization (vinylidene fluoride and carboxyl group-containing monomers, and other monomers copolymerized as necessary)
  • the amount is preferably 0.3 to 2 parts by weight.
  • a carboxyl group-containing vinylidene fluoride system obtained by adding a chain transfer agent such as ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate, carbon tetrachloride, etc. It is also possible to adjust the degree of polymerization of the polymer (B).
  • the amount used is usually 0.1 to 5 when 100 parts by weight of all monomers used for copolymerization (vinylidene fluoride, carboxyl group-containing monomers, and other monomers copolymerized as necessary) are used. Part by weight, preferably 0.5 to 3 parts by weight.
  • the total amount of monomers used for copolymerization is usually in the weight ratio of the total monomer: water.
  • the ratio is 1: 1 to 1:10, preferably 1: 2 to 1: 5, the polymerization is at a temperature of 10 to 80 ° C., the polymerization time is 10 to 100 hours, and the polymerization pressure is usually carried out under pressure. Preferably, it is 2.0 to 8.0 MPa-G.
  • a group-containing vinylidene fluoride polymer (B) can be obtained.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is produced by the method (2), for example, the following method can be used.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is produced by the method (2), first, vinylidene fluoride is polymerized or vinylidene fluoride is copolymerized with another monomer to obtain vinylidene fluoride. A polymer is obtained. The polymerization or copolymerization is usually performed by suspension polymerization or emulsion polymerization. In addition to the vinylidene fluoride polymer, a carboxyl group-containing polymer is obtained by polymerizing a carboxyl group-containing monomer or copolymerizing a carboxyl group-containing monomer and another monomer. The carboxyl group-containing polymer is usually obtained by emulsion polymerization or suspension polymerization.
  • the carboxyl group-containing vinylidene fluoride polymer (B) is obtained by grafting the carboxyl group-containing polymer onto the vinylidene fluoride polymer using the vinylidene fluoride polymer and the carboxyl group-containing polymer.
  • the grafting may be performed using a peroxide or may be performed using radiation.
  • a mixture of a vinylidene fluoride polymer and a carboxyl group-containing polymer is heated in the presence of a peroxide. It is done by processing.
  • the carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention has an inherent viscosity (logarithmic viscosity at 30 ° C. of a solution obtained by dissolving 4 g of resin in 1 liter of N, N-dimethylformamide. The same applies hereinafter).
  • a value in the range of 0.5 to 5.0 dl / g is preferable, and a value in the range of 1.1 to 4.0 dl / g is more preferable. If it is a viscosity within the said range, it can use suitably for the mixture for nonaqueous electrolyte secondary batteries.
  • the inherent viscosity ⁇ i is calculated by dissolving 80 mg of the carboxyl group-containing vinylidene fluoride polymer (B) in 20 ml of N, N-dimethylformamide and using an Ubbelote viscometer in a constant temperature bath at 30 ° C. Can be performed.
  • ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
  • ⁇ is the viscosity of the polymer solution
  • ⁇ 0 is the viscosity of the solvent N, N-dimethylformamide alone
  • C is 0.4 g / dl.
  • the carboxyl group-containing vinylidene fluoride polymer (B) has a polystyrene-equivalent weight average molecular weight measured by GPC usually in the range of 50,000 to 2,000,000, preferably in the range of 200,000 to 1,500,000. It is.
  • the carboxyl group-containing vinylidene fluoride polymer (B) has an absorbance ratio (I R ) represented by the following formula (1) when an infrared absorption spectrum is measured, in the range of 0.1 to 5.0. Preferably, it is 0.3 to 2.5. If I R is less than 0.1, there is a case where adhesion between the current collector becomes insufficient. On the other hand, if I R exceeds 5.0, electrolyte resistance of the resulting polymer tends to decrease. In addition, the measurement of the infrared absorption spectrum of this polymer is performed by measuring an infrared absorption spectrum about the film manufactured by hot-pressing this polymer.
  • I 1650-1800 I 3000-3100
  • I 1650-1800 is the absorbance from the carbonyl group which is detected in the range of 1650 ⁇ 1800cm -1
  • I 3000-3100 are derived from CH structures detected in the range of 3000 ⁇ 3100 cm -1 Absorbance.
  • I R becomes a measure of the abundance of the carbonyl group in the carboxyl group-containing vinylidene fluoride-based polymer (B), a measure of the abundance of the resulting carboxyl group.
  • the mixture for nonaqueous electrolyte secondary batteries of the present invention contains an electrode active material.
  • the electrode active material is not particularly limited, and conventionally known electrode active materials for negative electrodes can be used, and specific examples include carbon materials, metal / alloy materials, metal oxides, etc. Material is preferred.
  • the carbon material artificial graphite, natural graphite, non-graphitizable carbon, graphitizable carbon, or the like is used. Moreover, the said carbon material may be used individually by 1 type, or may use 2 or more types.
  • the energy density of the battery can be increased.
  • the artificial graphite can be obtained, for example, by carbonizing an organic material, heat-treating it at a high temperature, pulverizing and classifying it.
  • MAG series manufactured by Hitachi Chemical Co., Ltd.
  • MCMB manufactured by Osaka Gas
  • the specific surface area of the electrode active material is preferably 1 to 10 m 2 / g, and more preferably 2 to 6 m 2 / g.
  • the specific surface area is less than 1 m 2 / g, even when a conventional binder is used, the uneven distribution of the binder is unlikely to occur, so the effect of the present invention is small. If the specific surface area exceeds 10 m 2 / g, the amount of decomposition of the electrolytic solution increases and the initial irreversible capacity increases, which is not preferable.
  • the specific surface area of the electrode active material can be determined by a nitrogen adsorption method.
  • the mixture for nonaqueous electrolyte secondary batteries of the present invention contains an organic solvent.
  • the organic solvent those having an action of dissolving the unsaturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B) are used, and a solvent having polarity is preferably used.
  • Specific examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate.
  • N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the non-aqueous electrolyte secondary battery mixture of the present invention contains the unsaturated carboxylic acid polymer (A), a carboxyl group-containing vinylidene fluoride polymer (B), an electrode active material, and an organic solvent.
  • the mixture for a non-aqueous electrolyte secondary battery of the present invention includes an unsaturated carboxylic acid polymer (A) and a carboxyl group-containing vinylidene fluoride polymer (B), but the unsaturated carboxylic acid polymer (A) and
  • the unsaturated carboxylic acid polymer (A) is preferably 0.5 to 15% by weight, preferably 0.8 to 6% by weight, per 100% by weight of the total of the carboxyl group-containing vinylidene fluoride polymer (B). More preferably.
  • the binder resin is 0.5 to 15 weights per 100 parts by weight in total of the binder resin (unsaturated carboxylic acid polymer (A) and carboxyl group-containing vinylidene fluoride polymer (B)) and the electrode active material. Parts, preferably 1 to 10 parts by weight, and the active material is preferably 85 to 99.5 parts by weight, and more preferably 90 to 99 parts by weight. Further, when the total of the binder resin (unsaturated carboxylic acid polymer (A) and carboxyl group-containing vinylidene fluoride polymer (B)) and the electrode active material is 100 parts by weight, the organic solvent is 20 to 300 weights. Parts, preferably 50 to 200 parts by weight.
  • the mixture for a non-aqueous electrolyte secondary battery of the present invention is other than the unsaturated carboxylic acid polymer (A), the carboxyl group-containing vinylidene fluoride polymer (B), the electrode active material, and the organic solvent.
  • the component may be contained.
  • a conductive aid such as carbon black, a pigment dispersant such as polyvinylpyrrolidone, and the like may be included.
  • polymers other than the said unsaturated carboxylic acid polymer (A) and a carboxyl group-containing vinylidene fluoride polymer (B) may be included.
  • Examples of the other polymer include fluorides such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, and vinylidene fluoride-perfluoromethyl vinyl ether copolymer.
  • Examples include vinylidene polymers.
  • the unsaturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B) are usually used. It is contained in an amount of 25 parts by weight or less with respect to a total of 100 parts by weight.
  • the viscosity of the mixture for a non-aqueous electrolyte secondary battery of the present invention when measured with an E-type viscometer at 25 ° C. and a shear rate of 2 s ⁇ 1 is usually 2000 to 50000 mPa ⁇ s, preferably Is 5000 to 30000 mPa ⁇ s.
  • the method for producing the mixture for a non-aqueous electrolyte secondary battery of the present invention includes the unsaturated carboxylic acid polymer (A), the carboxyl group-containing vinylidene fluoride polymer (B), the electrode active material, and the organic solvent.
  • the order at the time of mixing is not specifically limited,
  • the said unsaturated carboxylic acid polymer (A) and a carboxyl group-containing vinylidene fluoride polymer (B) Dissolving in a part of the organic solvent to obtain a binder solution, adding the electrode active material and the remaining organic solvent to the binder solution, mixing by stirring, and obtaining a mixture for a non-aqueous electrolyte secondary battery,
  • the saturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B) are each dissolved in a part of an organic solvent to obtain two binder solutions. Ndoshi, was added blended binder solution in the electrode active material and the remaining organic solvent, stirring and mixing, a method may be mentioned of obtaining a nonaqueous electrolyte secondary battery mixture.
  • the electrode for a non-aqueous electrolyte secondary battery of the present invention is obtained by applying and drying the mixture for a non-aqueous electrolyte secondary battery on a current collector, and the current collector and for the non-aqueous electrolyte secondary battery And a layer formed from a mixture.
  • the electrode for a nonaqueous electrolyte secondary battery of the present invention is usually used as a negative electrode.
  • a layer formed from a mixture for a nonaqueous electrolyte secondary battery which is formed by applying and drying a mixture for a nonaqueous electrolyte secondary battery on a current collector, a mixture layer I write.
  • the current collector used in the present invention includes, for example, copper, and the shape thereof includes, for example, a metal foil, a metal net, and the like.
  • a copper foil is preferable.
  • the thickness of the current collector is usually 5 to 100 ⁇ m, preferably 5 to 20 ⁇ m.
  • the thickness of the mixture layer is usually 20 to 250 ⁇ m, preferably 20 to 150 ⁇ m.
  • the mixture for nonaqueous electrolyte secondary battery is applied to at least one surface, preferably both surfaces of the current collector.
  • the method for coating is not particularly limited, and examples thereof include a method using a bar coater, a die coater, or a comma coater.
  • drying performed after the coating is usually performed at a temperature of 50 to 150 ° C. for 1 to 300 minutes.
  • the pressure at the time of drying is not particularly limited, but it is usually carried out under atmospheric pressure or reduced pressure.
  • heat treatment may be performed after drying. When heat treatment is performed, it is usually performed at a temperature of 100 to 250 ° C. for 1 to 300 minutes. In addition, although the temperature of heat processing overlaps with the said drying, these processes may be a separate process and the process performed continuously.
  • press processing may be performed.
  • the pressing process it is normally performed at 1 to 200 MP-G. It is preferable to perform the press treatment because the electrode density can be improved.
  • the electrode for nonaqueous electrolyte secondary batteries of the present invention can be produced.
  • the layer structure of the mixture layer / current collector is Yes, when the mixture for a non-aqueous electrolyte secondary battery is applied on both sides of the current collector, it has a three-layer structure of a mixture layer / current collector / mixture layer.
  • the electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in peel strength between the current collector and the mixture layer by using the mixture for a non-aqueous electrolyte secondary battery, so that press, slit, winding, etc. In this process, cracks and peeling are unlikely to occur in the electrode, which is preferable because it leads to an improvement in productivity.
  • the electrode for a non-aqueous electrolyte secondary battery of the present invention is excellent in the peel strength between the current collector and the mixture layer as described above.
  • the peel strength between the current collector and the mixture layer is According to JIS K6854, it is usually 0.5 to 20 gf / mm, preferably 1 to 10 gf / mm when measured by a 180 ° peel test.
  • the electrode for a non-aqueous electrolyte secondary battery of the present invention has a mixture layer formed from the mixture for the non-aqueous electrolyte secondary battery, and the mixture layer suppresses uneven distribution of the binder. ing. Therefore, the peel strength between the current collector and the mixture layer is excellent.
  • Nonaqueous electrolyte secondary battery The non-aqueous electrolyte secondary battery of the present invention is characterized by having the non-aqueous electrolyte secondary battery electrode.
  • the nonaqueous electrolyte secondary battery of the present invention is not particularly limited except that it has the electrode for nonaqueous electrolyte secondary battery.
  • the electrode for a nonaqueous electrolyte secondary battery is usually used as a negative electrode, and conventionally known ones other than the negative electrode, such as a positive electrode and a separator, can be used.
  • Shodex KD-806M (made by Showa Denko KK) is used for the separation column
  • RI-930 (differential refractive index detector) made by JASCO Corporation is used for the detector
  • the flow rate of the eluent is 1 mL. / Min and column temperature of 40 ° C.
  • Na 2 HPO 4 / CH 3 CN 90/10 (weight ratio) was used as the eluent, and TSK standard POLY (ETHYLENE OXIDE) (standard polyethylene oxide) (Tosoh Corporation) was used as the standard polymer for the calibration curve. Used).
  • the specific surface area of the active material was measured by a nitrogen adsorption method.
  • Vm 1 / (v (1-x)
  • the specific surface area of the sample (active material) was calculated by the following formula.
  • Vm is an adsorption amount (cm 3 / g) necessary for forming a monomolecular layer on the sample surface
  • v is an actually measured adsorption amount (cm 3 / g)
  • x is a relative pressure.
  • the adsorption amount (v) of nitrogen on the active material at the liquid nitrogen temperature was measured as follows.
  • the sample tube is filled with the active material, and while flowing a helium gas containing nitrogen gas at a concentration of 20 mol%, the sample tube is cooled to ⁇ 196 ° C. to adsorb nitrogen to the active material.
  • the test tube is then returned to room temperature.
  • the amount of nitrogen desorbed from the sample was measured with a thermal conductivity detector, and was defined as the adsorption amount (v).
  • Example 1 (Preparation of non-aqueous electrolyte secondary battery mixture) 9.9 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.1 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (1).
  • a non-aqueous electrolyte secondary battery mixture (1) obtained by using a spacer and a bar coater so as to have a basis weight after drying of 150 g / m 2 was used as a current collector of copper having a thickness of 10 ⁇ m. It was applied on the foil. After drying at 110 ° C. in a nitrogen atmosphere, heat treatment was performed at 130 ° C. Subsequently, pressing is performed at 40 MPa, and the electrode layer for nonaqueous electrolyte secondary battery (1) having a bulk density of 1.6 g / cm 3 of the mixture layer formed from the mixture for nonaqueous electrolyte secondary battery (1). Got. The thickness of the mixture layer was calculated by subtracting the thickness of the current collector from the thickness of the electrode.
  • [Comparative Example 1] 10.0 g of the carboxyl group-containing vinylidene fluoride polymer (1) was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (c1). Except having used this binder solution (c1), it carried out similarly to Example 1 and obtained the mixture for nonaqueous electrolyte secondary batteries (c1) and the electrode for nonaqueous electrolyte secondary batteries (c1). The viscosity of the mixture for nonaqueous electrolyte secondary batteries (c1) was 12000 mPa ⁇ s.
  • Example 2 9.75 g of a carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.25 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (2). Except having used this binder solution (2), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (2) and the electrode for nonaqueous electrolyte secondary batteries (2) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (2) was 11800 mPa ⁇ s.
  • Example 3 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.5 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (3). Except having used this binder solution (3), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (3) and the electrode for nonaqueous electrolyte secondary batteries (3) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (3) was 11500 mPa ⁇ s.
  • Example 4 9.0 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 1.0 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (4). Except having used this binder solution (4), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (4) and the electrode for nonaqueous electrolyte secondary batteries (4) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (4) was 11500 mPa ⁇ s.
  • Example 5 8.7 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 1.3 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (5). Except having used this binder solution (5), it carried out similarly to Example 1 and obtained the mixture (5) for nonaqueous electrolyte secondary batteries, and the electrode (5) for nonaqueous electrolyte secondary batteries. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (5) was 11000 mPa ⁇ s.
  • Example 6 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 15,000 (trade name “Julimer AC-10P”, manufactured by Nippon Pure Chemical Co., Ltd., carboxyl group amount: 1. (4 ⁇ 10 ⁇ 2 mol / g) (0.5 g) was dissolved in N-methyl-2-pyrrolidone (90 g) to obtain a 10 wt% binder solution (6). Except having used this binder solution (6), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (6) and the electrode for nonaqueous electrolyte secondary batteries (6) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (6) was 12000 mPa ⁇ s.
  • Example 7 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 25,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.5 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (7). Except having used this binder solution (7), it carried out similarly to Example 1 and obtained the mixture (7) for nonaqueous electrolyte secondary batteries, and the electrode (7) for nonaqueous electrolyte secondary batteries. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (7) was 12300 mPa ⁇ s.
  • Example 8 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 73,000 (trade name “Julimer AC-10LP”, manufactured by Nippon Pure Chemical Co., Ltd., carboxyl group amount: 1. (4 ⁇ 10 ⁇ 2 mol / g) (0.5 g) was dissolved in N-methyl-2-pyrrolidone (90 g) to obtain a 10 wt% binder solution (8). Except having used this binder solution (8), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (8) and the electrode for nonaqueous electrolyte secondary batteries (8) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (8) was 12500 mPa ⁇ s.
  • [Comparative Example 10] 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 250,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.5 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (c10). Except having used this binder solution (c10), it carried out like Example 1 and the mixture for nonaqueous electrolyte secondary batteries (c10) and the electrode for nonaqueous electrolyte secondary batteries (c10) were obtained. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (c10) was 13000 mPa ⁇ s.
  • Example 2 The same procedure as in Example 1 was conducted except that the binder solution (c12) was used and that N-methyl-2-pyrrolidone for adjusting the viscosity of the mixture was changed to 3 g, and a mixture for a nonaqueous electrolyte secondary battery ( c12) and a non-aqueous electrolyte secondary battery electrode (c12) were obtained.
  • the viscosity of the mixture for nonaqueous electrolyte secondary batteries (c12) was 8500 mPa ⁇ s.
  • Example 2 The same procedure as in Example 1 was performed except that the nonaqueous electrolyte secondary battery mixture (c13) was used to obtain a nonaqueous electrolyte secondary battery electrode (c13).
  • the viscosity of the mixture for nonaqueous electrolyte secondary batteries (c13) was 13500 mPa ⁇ s.
  • Example 9 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.5 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (9).
  • Example 2 The same procedure as in Example 1 was performed except that the non-aqueous electrolyte secondary battery mixture (9) was used to obtain a non-aqueous electrolyte secondary battery electrode (9).
  • [Comparative Example 14] 10.0 g of the carboxyl group-containing vinylidene fluoride polymer (1) was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (c14). 8 g of the obtained binder solution (c14), 9.2 g of spherical natural graphite (produced in China, average particle size 24 ⁇ m, specific surface area 5.4 m 2 / g), and N-methyl-2-pyrrolidone 5 for adjusting the mixture viscosity .8 g was mixed with stirring to obtain a nonaqueous electrolyte secondary battery mixture (c14). The viscosity of the mixture for nonaqueous electrolyte secondary batteries (c14) was 13000 mPa ⁇ s.
  • Example 2 The same procedure as in Example 1 was performed except that the nonaqueous electrolyte secondary battery mixture (c14) was used to obtain a nonaqueous electrolyte secondary battery electrode (c14).
  • Example 10 9.5 g of carboxyl group-containing vinylidene fluoride polymer (1) and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group amount: 1.4 ⁇ 10 ⁇ 2 mol / g) 0.5 g was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a 10 wt% binder solution (10).
  • Example 2 The same procedure as in Example 1 was performed except that the non-aqueous electrolyte secondary battery mixture (10) was used to obtain a non-aqueous electrolyte secondary battery electrode (10).
  • the gauge pressure was set to 7 MPa, the electrode on which the damplon tape was attached was pressed for 20 seconds, and then the mixture layer was peeled from the current collector. Similar to the fluorine strength of the electrode surface, the release surface of the mixture layer from which the current collector has been peeled off and the release surface of the current collector from which the mixture layer has been peeled off from the mixture layer. The fluorine intensity was measured by this method.
  • release surface of the mixture layer from which the current collector has been peeled off is also referred to as the “release surface of the mixture layer”, and the current collector layer from which the mixture layer has been peeled off This peeling surface is also referred to as a “current collector peeling surface”.
  • Tables 1 and 2 show the compositions of the binder solution and the non-aqueous electrolyte secondary battery mixture used in Examples and Comparative Examples, the thickness of the obtained electrode mixture layer, and the electrode evaluation results.

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Abstract

L'invention concerne une couche de mélange et un mélange destiné à une pile rechargeable à électrolyte non aqueux, qui présente une excellente résistance au décollement par rapport à un collecteur de puissance, permet d'obtenir une productivité élevée dans la fabrication d'une électrode de pile rechargeable non aqueuse et d'une pile rechargeable non aqueuse, et permet d'éviter une mauvaise distribution d'un agent de liaison dans la couche de mélange, lors de la fabrication de l'électrode. Le mélange pour pile rechargeable non aqueuse contient au moins un type de polymère d'acide carboxylique insaturé (A), sélectionné entre un acide polyacrylique et un acide polyméthacrylique, un polymère de fluorure de vinylidène contenant un carboxyle (B), une matière active d'électrode, et présente un poids moléculaire moyen en poids de 1000 - 150000 de conversion d'oxyde de polyéthylène, mesuré par chromatographie par perméation de gel du polymère d'acide carboxylique insaturé (A).
PCT/JP2011/055337 2010-03-30 2011-03-08 Mélange pour pile rechargeable à électrolyte non aqueux, électrode destinée à celle-ci et pile rechargeable à électrolyte non aqueux WO2011122261A1 (fr)

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JP2012508179A JP5684235B2 (ja) 2010-03-30 2011-03-08 非水電解質二次電池用合剤、非水電解質二次電池用電極および非水電解質二次電池
KR1020127018065A KR101464841B1 (ko) 2010-03-30 2011-03-08 비수 전해질 ２ 차 전지용 합제, 비수 전해질 ２ 차 전지용 전극 및 비수 전해질 ２ 차 전지

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KR20150042147A (ko) * 2012-08-10 2015-04-20 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물
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WO2016038682A1 (fr) * 2014-09-09 2016-03-17 株式会社 東芝 Batterie à électrolyte non aqueux et bloc-batterie
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JP2018529206A (ja) * 2015-09-29 2018-10-04 エー１２３ システムズ エルエルシーＡ１２３ Ｓｙｓｔｅｍｓ ＬＬＣ エネルギー貯蔵装置用の混合バインダーを有する高容量アノード電極
JP2018535533A (ja) * 2015-11-24 2018-11-29 アルケマ フランス 金属への固定が可能なポリビニリデンフルオライドを含有するバインダー及び関連するリチウムイオンバッテリー用電極
WO2019207833A1 (fr) 2018-04-26 2019-10-31 株式会社クレハ Particules
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KR20150042147A (ko) * 2012-08-10 2015-04-20 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물
KR102142441B1 (ko) 2012-08-10 2020-08-07 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물
WO2014065407A1 (fr) * 2012-10-26 2014-05-01 和光純薬工業株式会社 Liant pour une pile au lithium, composition pour produire une électrode et électrode
US10862127B2 (en) 2012-10-26 2020-12-08 Tokyo University Of Science Foundation Binder for lithium cell, composition for producing electrode, and electrode
US10044040B2 (en) 2012-10-26 2018-08-07 Tokyo University Of Science Foundation Binder for lithium cell, composition for producing electrode, and electrode
WO2014109366A1 (fr) * 2013-01-11 2014-07-17 日立マクセル株式会社 Batterie secondaire à électrolyte non aqueux
JP2015125988A (ja) * 2013-12-27 2015-07-06 トヨタ自動車株式会社 リチウムイオン電池用負極の製造方法
WO2016038682A1 (fr) * 2014-09-09 2016-03-17 株式会社 東芝 Batterie à électrolyte non aqueux et bloc-batterie
JPWO2016038682A1 (ja) * 2014-09-09 2017-04-27 株式会社東芝 非水電解質電池及び電池パック
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JP2018529206A (ja) * 2015-09-29 2018-10-04 エー１２３ システムズ エルエルシーＡ１２３ Ｓｙｓｔｅｍｓ ＬＬＣ エネルギー貯蔵装置用の混合バインダーを有する高容量アノード電極
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US20180366733A1 (en) 2015-12-10 2018-12-20 Kaneka Corporation Nonaqueous electrolyte secondary battery
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JPWO2017098682A1 (ja) * 2015-12-10 2018-09-27 株式会社カネカ 非水電解液二次電池
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