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WO2010074041A1 - Mélange pour produire une électrode négative destinée à une batterie rechargeable à électrolyte non aqueux, électrode négative pour batterie rechargeable à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux - Google Patents

Mélange pour produire une électrode négative destinée à une batterie rechargeable à électrolyte non aqueux, électrode négative pour batterie rechargeable à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux Download PDF

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Publication number
WO2010074041A1
WO2010074041A1 PCT/JP2009/071261 JP2009071261W WO2010074041A1 WO 2010074041 A1 WO2010074041 A1 WO 2010074041A1 JP 2009071261 W JP2009071261 W JP 2009071261W WO 2010074041 A1 WO2010074041 A1 WO 2010074041A1
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Prior art keywords
vinylidene fluoride
electrolyte secondary
polar group
secondary battery
negative electrode
Prior art date
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PCT/JP2009/071261
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English (en)
Japanese (ja)
Inventor
綾香 田上
充康 佐久間
信男 阿彦
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Kureha Corp
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Kureha Corp
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Priority to CN2009801409164A priority Critical patent/CN102187503A/zh
Priority to KR1020117008500A priority patent/KR101298300B1/ko
Priority to JP2010544060A priority patent/JP5626791B2/ja
Publication of WO2010074041A1 publication Critical patent/WO2010074041A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 negative electrode mixture for a nonaqueous electrolyte secondary battery, a negative 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.
  • a binder binder
  • a powdered electrode forming material such as an electrode active material and a conductive additive added as necessary.
  • an electrode mixture obtained by dissolving or dispersing in a suitable solvent is obtained by coating and drying on a current collector to form a mixture layer.
  • the binder for example, it is necessary to have durability against a non-aqueous electrolyte obtained by dissolving an electrolyte such as LiPF 6 or LiClO 4 in a non-aqueous solvent such as ethylene carbonate or propylene carbonate, and the specific resistance is small.
  • the thin film forming property is required to be good.
  • a vinylidene fluoride polymer is generally used as the binder.
  • Patent Document 1 discloses a vinylidene fluoride copolymer obtained by copolymerizing vinylidene fluoride and an unsaturated dibasic acid monoester. Patent Document 1 aims to provide a vinylidene fluoride polymer that has good adhesion to a base material such as metal, is excellent in chemical resistance, and can be produced by aqueous polymerization.
  • a base material such as metal
  • the electrode mixture used as a binder for manufacturing an electrode is described, the components contained in the electrode mixture other than the polymer are not particularly limited.
  • Patent Document 2 discloses adding an acid to a slurry applied to a current collector as a method for producing a battery electrode having excellent peel strength between the current collector and a mixture layer. Patent Document 2 describes that an organic acid is preferable as the acid, and a carboxylic acid is more preferable.
  • the present invention has been made in view of the above-described problems of the prior art, and has a non-aqueous electrolyte that is excellent in peel strength between a mixture layer and a current collector when a negative electrode for a non-aqueous electrolyte secondary battery is manufactured.
  • An object is to provide a negative electrode mixture for a secondary battery, a negative electrode for a non-aqueous electrolyte secondary battery obtained by applying and drying the mixture to a current collector, and a non-aqueous electrolyte secondary battery having the negative electrode. To do.
  • the present inventors have developed a non-aqueous electrolyte secondary battery containing a specific polymer containing a chlorine atom and a specific polymer containing a polar group.
  • the negative electrode for non-aqueous electrolyte secondary batteries produced using the negative electrode mixture was found to have excellent peel strength between the mixture layer and the current collector, and the present invention was completed.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a polar group-containing vinylidene fluoride polymer, a chlorine atom-containing vinylidene fluoride polymer, an electrode active material, and an organic solvent,
  • the chlorine atom-containing vinylidene fluoride polymer is characterized by containing 0.3 to 5% by weight of chlorine atoms per 100% by weight of the polymer.
  • the polar group of the polar group-containing vinylidene fluoride polymer is preferably at least one polar group selected from the group consisting of a carboxyl group and a carboxylic anhydride group. Further, when the polar group of the polar group-containing vinylidene fluoride polymer is at least one polar group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, the polar group-containing fluorine is contained.
  • the absorbance ratio (I R ) represented by the following formula (1) when the infrared absorption spectrum of the vinylidene chloride polymer is measured is more preferably in the range of 0.10 to 1.5.
  • I R I 1750 / I 3025 (1) (In the above formula (1), I 1750 is the absorbance of 1750 cm -1, I 3025 is the absorbance of 3025cm -1.)
  • the chlorine atom-containing vinylidene fluoride polymer is a copolymer of vinylidene fluoride obtained by copolymerizing 90 to 99 parts by weight of vinylidene fluoride and 1 to 10 parts by weight of a chlorine atom-containing monomer (provided that the fluoride The total of vinylidene and chlorine atom-containing monomer is 100 parts by weight).
  • the chlorine atom-containing monomer is chlorotrifluoroethylene.
  • the electrode active material is preferably a carbon material.
  • the negative electrode for a nonaqueous electrolyte secondary battery according to the present invention is obtained by applying and drying the negative electrode mixture for a nonaqueous electrolyte secondary battery on a current collector.
  • the nonaqueous electrolyte secondary battery of the present invention has the above-described negative electrode for a nonaqueous electrolyte secondary battery.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a polar group-containing vinylidene fluoride polymer and a chlorine atom-containing vinylidene fluoride polymer, and thus is manufactured using the mixture.
  • the negative electrode for a water electrolyte secondary battery is excellent in the peel strength between the mixture layer and the current collector.
  • FIG. 3 is a diagram showing an IR spectrum of a polar group-containing vinylidene fluoride polymer- (1) used in Examples.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a polar group-containing vinylidene fluoride polymer, a chlorine atom-containing vinylidene fluoride polymer, an electrode active material, and an organic solvent, and contains the chlorine atom
  • the vinylidene fluoride polymer contains 0.3 to 5% by weight of chlorine atoms per 100% by weight of the polymer.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery 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 negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention contains a polar group-containing vinylidene fluoride polymer as a binder resin.
  • the polar group-containing vinylidene fluoride polymer is a polymer containing a polar group in a polymer and obtained using at least vinylidene fluoride as a monomer.
  • the polar group-containing vinylidene fluoride polymer is a polymer usually obtained using a monomer containing vinylidene fluoride and a polar group, and other monomers may be used.
  • a monomer containing a polar group in the molecule is also referred to as a polar group-containing monomer.
  • the polar group means an atomic group containing an atom having an electronegativity higher than that of carbon such as nitrogen, oxygen, sulfur, or phosphorus. That is, simple atoms such as fluorine and chlorine are not polar groups in the present invention.
  • Examples of the polar group contained in the polar group-containing vinylidene fluoride polymer used in the present invention include a carboxyl group, an epoxy group, a hydroxy group, a sulfonic acid group, a carboxylic acid anhydride group, and an amino group. Carboxylic anhydride groups are preferred.
  • the polar group-containing vinylidene fluoride polymer used in the present invention contains at least one of these polar groups, and may contain two or more.
  • a vinylidene fluoride polymer containing at least one polar group selected from the group consisting of a carboxyl group and a carboxylic anhydride group is an adhesive performance and availability aspect. To preferred.
  • the polar group-containing vinylidene fluoride polymer used in the present invention may be used alone or in combination of two or more.
  • the polar group-containing vinylidene fluoride polymer is at least one polar group selected from the group consisting of a carboxyl group and a carboxylic anhydride group
  • the polar group-containing vinylidene fluoride polymer Is a polymer that usually has 80 or more, preferably 85 or more parts by weight of structural units derived from vinylidene fluoride per 100 parts by weight of the polymer.
  • the polar group-containing vinylidene fluoride polymer used in the present invention is usually (1) a method of copolymerizing vinylidene fluoride and a polar group-containing monomer and, if necessary, other monomers (hereinafter referred to as the method of (1)).
  • the polar group-containing vinylidene fluoride polymer used in the present invention has a polar group, the adhesion to the current collector is improved as compared with polyvinylidene fluoride not having a polar group.
  • the polar group-containing vinylidene fluoride polymer has chemical resistance equivalent to that of polyvinylidene fluoride having no polar group.
  • the method (1) is preferable from the viewpoint of the number of steps and production cost.
  • the polar group-containing vinylidene fluoride polymer used in the present invention usually comprises 80 to 99.9 parts by weight of vinylidene fluoride and 0.1 to 20 parts by weight of a polar group-containing monomer (provided that the vinylidene fluoride and the polar group-containing monomer are Vinylidene fluoride copolymer obtained by copolymerization of 100 parts by weight in total.
  • the polar group-containing vinylidene fluoride polymer may be a polymer obtained by copolymerizing another monomer in addition to the vinylidene fluoride and the polar group-containing monomer. When other monomers are used, 0.1 to 20 parts by weight of other monomers are usually used when the total of the vinylidene fluoride and the polar group-containing monomer is 100 parts by weight.
  • the polar group-containing monomer is usually a carboxyl group.
  • a monomer containing at least one polar group selected from the group consisting of carboxylic anhydride groups, and at least one selected from the group consisting of carboxyl group-containing monomers and carboxylic anhydride group-containing monomers It is preferable to use a monomer.
  • the polar group-containing vinylidene fluoride polymer is 90 to 99.9 wt.
  • 0.1 to 10 parts by weight of at least one monomer selected from the group consisting of a monomer, a carboxyl group-containing monomer, and a carboxylic acid anhydride group-containing monomer provided that vinylidene fluoride, a carboxyl group-containing monomer, and a carboxylic acid anhydride
  • carboxyl group-containing monomer unsaturated monobasic acids, unsaturated dibasic acids, monoesters of unsaturated dibasic acids, and the like are preferable, and monoesters of unsaturated dibasic acids and unsaturated dibasic acids are more preferable.
  • Examples of the unsaturated monobasic acid include acrylic 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.
  • maleic acid citraconic acid
  • maleic acid monomethyl ester maleic acid monomethyl ester
  • citraconic acid monomethyl ester maleic acid monomethyl ester
  • Examples of the carboxylic acid anhydride group-containing monomer include unsaturated dibasic acid anhydrides, and examples of the unsaturated dibasic acid anhydride groups include maleic anhydride and citraconic anhydride.
  • the polar group-containing vinylidene fluoride polymer of the present invention is a polymer having a polar group usually derived from a polar group-containing monomer.
  • a carboxyl group-containing monomer is used as the polar group-containing monomer
  • a carboxyl group-containing vinylidene fluoride polymer is usually obtained as the polar group-containing vinylidene fluoride polymer.
  • the polar group-containing vinylidene fluoride polymer has a carboxyl group obtained by hydrolysis of the carboxylic acid anhydride group. And may have a carboxylic anhydride group.
  • the other monomer that can be used in the present invention means a monomer other than vinylidene fluoride and a polar group-containing monomer.
  • the other monomer include a fluorine-based monomer copolymerizable with vinylidene fluoride or the like. Examples thereof include hydrocarbon monomers such as ethylene and propylene.
  • the fluorine-based monomer copolymerizable with vinylidene fluoride include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.
  • 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.
  • suspending agents such as methylcellulose, methoxylated methylcellulose, propoxylated methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, gelatin, etc. (Vinylidene fluoride and polar group-containing monomer, other monomer 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 polar group-containing monomers, and other monomers copolymerized as necessary) The amount is preferably 0.3 to 2 parts by weight.
  • a polar 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.
  • the amount used is usually 0.1 to 5 when 100 parts by weight of all monomers used for copolymerization (vinylidene fluoride, polar group-containing monomer, and other monomers copolymerized as required) are used. Part by weight, preferably 0.5 to 3 parts by weight.
  • the total amount of monomers used for copolymerization is 1: 1 to 1:10, preferably 1: 2 to 1: 5, the polymerization is performed at a temperature of 10 to 80 ° C., the polymerization time is 10 to 100 hours, and the pressure during the polymerization is usually performed under pressure, The pressure is preferably 2.0 to 8.0 MPa-G.
  • the polar group-containing vinylidene fluoride polymer is produced by the method (2), it can be carried out, for example, by the following method.
  • a polar group-containing vinylidene fluoride polymer is produced by the method (2), first, vinylidene fluoride is polymerized or vinylidene fluoride is copolymerized with another monomer to obtain a vinylidene fluoride polymer. Get.
  • the polymerization or copolymerization is usually performed by suspension polymerization or emulsion polymerization.
  • a polar group-containing polymer is obtained by polymerizing a polar group-containing monomer or copolymerizing a polar group-containing monomer and another monomer.
  • the polar group-containing polymer is usually obtained by emulsion polymerization or suspension polymerization.
  • the polar group-containing vinylidene fluoride polymer can be obtained by grafting the polar group-containing polymer onto the vinylidene fluoride-based polymer using the above-mentioned vinylidene fluoride-based polymer and the polar group-containing polymer. .
  • the grafting may be carried out using a peroxide or using radiation.
  • a mixture of a vinylidene fluoride polymer and a polar group-containing polymer is heated in the presence of the peroxide. It is done by processing.
  • the polar group-containing vinylidene fluoride polymer 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 ⁇ 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 the viscosity within the said range, it can use suitably for the negative mix for nonaqueous electrolyte secondary batteries.
  • the inherent viscosity ⁇ i is calculated by dissolving 80 mg of a polar group-containing vinylidene fluoride polymer in 20 ml of N, N-dimethylformamide and using an Ubbelote viscometer in a constant temperature bath at 30 ° C. Can do.
  • ⁇ 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 weight average molecular weight of the polar group-containing vinylidene fluoride polymer determined by GPC is usually in the range of 50,000 to 1,500,000.
  • the polar group-containing vinylidene fluoride polymer is a vinylidene fluoride polymer containing at least one polar group selected from the group consisting of a carboxyl group and a carboxylic anhydride group
  • the absorbance ratio (I R ) represented by the following formula (1) when the infrared absorption spectrum of the polymer is measured is preferably in the range of 0.10 to 1.5.
  • 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 R I 1750 / I 3025 (1) (In the above formula (1), I 1750 is the absorbance of 1750 cm -1, I 3025 is the absorbance of 3025cm -1.) In the infrared absorption spectrum, the carbonyl group has an absorption band at 1650 to 1800 cm ⁇ 1 .
  • I 1750 is derived from a carbonyl group
  • I 3025 is derived from a C—H structure. Therefore, I R is the measure of the abundance of the carbonyl group of the polar group-containing vinylidene fluoride polymer.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a chlorine atom-containing vinylidene fluoride polymer as a binder resin.
  • the chlorine atom-containing vinylidene fluoride polymer is a polymer containing a chlorine atom in a polymer and obtained using at least vinylidene fluoride as a monomer.
  • the chlorine atom-containing vinylidene fluoride polymer used in the present invention contains 0.3 to 5% by weight of chlorine atoms per 100% by weight of the polymer.
  • the chlorine atom-containing vinylidene fluoride polymer is a polymer usually obtained using a monomer containing vinylidene fluoride and a chlorine atom, and other monomers may be used.
  • a monomer containing a chlorine atom in the molecule is also referred to as a chlorine atom-containing monomer.
  • the chlorine atom-containing vinylidene fluoride polymer used in the present invention may be used alone or in combination of two or more.
  • the chlorine atom-containing vinylidene fluoride polymer used in the present invention has a chlorine atom, adhesion to the current collector is improved as compared with polyvinylidene fluoride having no chlorine atom.
  • the chlorine atom-containing vinylidene fluoride polymer has chemical resistance equivalent to that of polyvinylidene fluoride having no chlorine atom.
  • the polar group-containing vinylidene fluoride polymer used in the present invention is usually 90 to 99 parts by weight of vinylidene fluoride and 1 to 10 parts by weight of a chlorine atom-containing monomer (provided that the total of vinylidene fluoride and chlorine atom-containing monomer is 100 weights).
  • the chlorine atom-containing vinylidene fluoride polymer may be a polymer obtained by copolymerizing another monomer in addition to the vinylidene fluoride and the chlorine atom-containing monomer. When other monomers are used, 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 chlorine atom-containing monomers is 100 parts by weight.
  • chlorotrifluoroethylene is usually used as the chlorine atom-containing monomer.
  • the other monomer that can be used in the present invention means a monomer other than vinylidene fluoride and a polar group-containing monomer.
  • the other monomer include a fluorine-based monomer copolymerizable with vinylidene fluoride or the like. Examples thereof include hydrocarbon monomers such as ethylene and propylene.
  • the fluorine-based monomer copolymerizable with vinylidene fluoride include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.
  • the said other monomer may be used individually by 1 type, and may use 2 or more types.
  • the chlorine atom-containing vinylidene fluoride polymer used in the present invention is usually produced by a method of copolymerizing vinylidene fluoride and a chlorine atom-containing monomer, and if necessary, other monomers.
  • suspension polymerization As the copolymerization method, suspension polymerization, emulsion polymerization, solution polymerization and the like can be adopted, but aqueous suspension polymerization and emulsion polymerization are preferred from the viewpoint of ease of post-treatment, and aqueous suspension polymerization. Is particularly preferred.
  • suspending agents such as methylcellulose, methoxylated methylcellulose, propoxylated methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, gelatin, etc. (Vinylidene fluoride and a chlorine atom-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 chlorine atom-containing monomers, and other monomers copolymerized as necessary) The amount is preferably 0.3 to 2 parts by weight.
  • a polar 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.
  • the amount used is usually 0.1 to 5 when 100 parts by weight of all monomers used for copolymerization (vinylidene fluoride, chlorine atom-containing monomers, and other monomers copolymerized as required) are used. Part by weight, preferably 0.5 to 3 parts by weight.
  • the amount of all monomers used for copolymerization is 1: 1 to 1:10, preferably 1: 2 to 1: 5, the polymerization is performed at a temperature of 10 to 80 ° C., the polymerization time is 10 to 100 hours, and the pressure during the polymerization is usually performed under pressure, The pressure is preferably 2.0 to 8.0 MPa-G.
  • the chlorine atom-containing vinylidene fluoride polymer used in the present invention contains 0.3 to 5% by weight, preferably 0.7 to 3% by weight, of chlorine atoms per 100% by weight of the polymer.
  • the chlorine atom content of the chlorine atom-containing vinylidene fluoride polymer was determined by ion chromatography using a test solution obtained by burning the chlorine atom-containing vinylidene fluoride polymer according to the flask combustion method (JIS K7229). Among the chromatograms obtained, the peak area of the chloride ion chromatogram can be obtained and obtained by the absolute calibration curve method.
  • the chlorine atom-containing vinylidene fluoride polymer 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 ⁇ 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 the viscosity within the said range, it can use suitably for the negative mix for nonaqueous electrolyte secondary batteries.
  • the inherent viscosity ⁇ i is calculated by dissolving 80 mg of a chlorine atom-containing vinylidene fluoride polymer in 20 ml of N, N-dimethylformamide and using an Ubbelote viscometer in a constant temperature bath at 30 ° C. Can do.
  • ⁇ 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 chlorine atom-containing vinylidene fluoride polymer usually has a weight average molecular weight determined by GPC (gel permeation chromatography) in the range of 50,000 to 1,500,000.
  • the negative electrode is excellent in peel strength between the mixture layer and the current collector.
  • the reason why the peel strength is excellent is not clear, but some of the chlorine atoms contained in the chlorine atom-containing vinylidene fluoride polymer are eliminated, reacting with the surface of the current collector, and containing a polar group at the reaction point
  • the present inventors estimated that the peel strength is excellent by reacting polar groups such as a carboxyl group and a carboxylic anhydride group of the vinylidene fluoride polymer.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention it is necessary to use a chlorine atom-containing vinylidene fluoride polymer and a polar group-containing vinylidene fluoride polymer in combination. It is preferable to use chlorotrifluoroethylene as the chlorine atom-containing monomer because the negative electrode is particularly excellent in peel strength between the mixture layer and the current collector.
  • the peel strength between the mixture layer and the current collector can be improved in the negative electrode for nonaqueous electrolyte secondary batteries. Compared to a mixture, it is effective in solving problems of electrode cracking and peeling during electrode production.
  • the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention contains an organic solvent.
  • the organic solvent those having an action of dissolving the polar group-containing vinylidene fluoride polymer and the chlorine atom-containing vinylidene fluoride polymer are used, and the solvent is preferably polar.
  • organic solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea , Triethyl phosphate, trimethyl phosphate and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-dimethylsulfoxide are preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains the above-mentioned polar group-containing vinylidene fluoride polymer, chlorine atom-containing vinylidene fluoride polymer, electrode active material, and organic solvent.
  • the content of each component of the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention is such that the polar group-containing vinylidene fluoride polymer and the chlorine atom-containing vinylidene fluoride polymer weight are usually based on 100 parts by weight of the electrode active material.
  • the total of the combination is 1 to 25 parts by weight
  • the organic solvent is 20 to 300 parts by weight
  • the total of the polar group-containing vinylidene fluoride polymer and the chlorine atom-containing vinylidene fluoride polymer is preferably 1 to 20 parts by weight.
  • the organic solvent is 70 to 200 parts by weight.
  • the weight ratio of the polar group-containing vinylidene fluoride polymer to the chlorine atom-containing vinylidene fluoride polymer is usually 5:95 to 95: 5, preferably 20:80 to 80:20. .
  • the electrode mixture layer and the current collector are collected.
  • the peel strength from the body can be further improved, and when producing a negative electrode for a non-aqueous electrolyte secondary battery, the coating property when applying a negative electrode mixture for a non-aqueous electrolyte secondary battery to the current collector is improved. Also excellent.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery comprises other components other than the polar group-containing vinylidene fluoride polymer, chlorine atom-containing vinylidene fluoride polymer, electrode active material and organic solvent. You may contain. As other components, a conductive aid such as carbon black, a pigment dispersant such as polyvinylpyrrolidone, and the like may be included. As said other component, polymers other than a polar group containing vinylidene fluoride polymer and a chlorine atom containing vinylidene fluoride polymer 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 total weight of the polar group-containing vinylidene fluoride polymer and the chlorine atom-containing vinylidene fluoride polymer is usually 100 weights. It is contained in an amount of 25 parts by weight or less based on parts.
  • the viscosity of the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention when measured using an E-type viscometer at 25 ° C. and a shear rate of 2 s ⁇ 1 is usually 2000 to 50000 mPa ⁇ s, Preferably, it is 5000 to 30000 mPa ⁇ s.
  • the method for producing a negative electrode mixture for a non-aqueous electrolyte secondary battery according to the present invention comprises uniformly mixing the polar group-containing vinylidene fluoride polymer, the chlorine atom-containing vinylidene fluoride polymer, the electrode active material, and the organic solvent. What is necessary is just to mix so that it may become a slurry, The order at the time of mixing is not specifically limited, For example, the said polar group containing vinylidene fluoride polymer and a chlorine atom containing vinylidene fluoride polymer are made into a part of organic solvent.
  • Dissolving obtaining a binder solution, adding an electrode active material and the remaining organic solvent to the binder solution, stirring and mixing, and obtaining a negative electrode mixture for a non-aqueous electrolyte secondary battery, the polar group-containing vinylidene fluoride After dissolving the polymer and the chlorine atom-containing vinylidene fluoride polymer in a part of the organic solvent, the two binder solutions are blended, and the electrode active material and the binder solution are blended.
  • a method may be mentioned of obtaining a non-aqueous electrolyte secondary battery negative electrode mixture.
  • the negative electrode for a non-aqueous electrolyte secondary battery of the present invention is obtained by applying and drying the negative electrode mixture for a non-aqueous electrolyte secondary battery on a current collector, and the current collector and the non-aqueous electrolyte secondary battery And a layer formed from the negative electrode mixture.
  • coating and drying the negative mix for nonaqueous electrolyte secondary batteries to a collector is described as a mixture layer.
  • 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 negative electrode mixture for a non-aqueous 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.
  • the negative electrode for nonaqueous electrolyte secondary batteries of the present invention can be produced.
  • a layer structure of the negative electrode for non-aqueous electrolyte secondary batteries when the negative electrode mixture for non-aqueous electrolyte secondary batteries is applied to one surface of the current collector, a two-layer structure of a mixture layer / current collector When the negative electrode mixture for a nonaqueous electrolyte secondary battery is applied to both sides of the current collector, it has a three-layer structure of a mixture layer / current collector / mixture layer.
  • the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is excellent in the peel strength between the current collector and the mixture layer by using the negative electrode mixture for a non-aqueous electrolyte secondary battery. It is preferable because the electrode is less likely to be cracked or peeled off in the process, etc., leading to improvement in productivity.
  • the negative 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.
  • Nonaqueous electrolyte secondary battery The nonaqueous electrolyte secondary battery of the present invention is characterized by having the negative electrode for a nonaqueous electrolyte secondary battery.
  • the non-aqueous electrolyte secondary battery of the present invention is not particularly limited as long as it has the negative electrode for non-aqueous electrolyte secondary batteries, and a part other than the negative electrode, for example, a positive electrode, a separator, etc., use a conventionally known one. Can do.
  • the polymerization yield was 85% by weight, and the inherent viscosity of the obtained polar group-containing vinylidene fluoride polymer- (1) was 2.1 dl / g.
  • the polymerization yield was 90% by weight, and the inherent viscosity of the obtained chlorine atom-containing vinylidene fluoride polymer- (1) was 2.0 dl / g.
  • the polymerization yield was 90% by weight, and the inherent viscosity of the obtained polyvinylidene fluoride- (1) was 2.0 dl / g.
  • the polymerization yield was 90% by weight, and the inherent viscosity of the obtained vinylidene fluoride-hexafluoropropylene copolymer- (1) was 2.1 dl / g.
  • the polymerization yield was 85% by weight, and the inherent viscosity of the obtained vinylidene fluoride-trifluoroethylene copolymer- (1) was 1.8 dl / g.
  • the test liquid obtained by burning the chlorine atom-containing vinylidene fluoride polymer- (1) was analyzed by ion chromatography. The peak area of the ion chromatogram was determined, and the chlorine content of the chlorine atom-containing vinylidene fluoride polymer- (1) was determined by an absolute calibration curve method.
  • the thus obtained chlorine atom-containing vinylidene fluoride polymer- (1) was 2.1% by weight per 100% by weight of the polymer.
  • the chlorine atom content of the polar group-containing vinylidene fluoride polymer- (1) obtained by the same method was 0% by weight per 100% by weight of the polymer.
  • the chlorine atom content of polyvinylidene fluoride- (1) obtained by the same method was 0% by weight per 100% by weight of the polymer.
  • the chlorine atom content of vinylidene fluoride-hexafluoropropylene copolymer (1) obtained by the same method was 0% by weight per 100% by weight of the polymer.
  • the chlorine atom content of vinylidene fluoride-trifluoroethylene copolymer- (1) obtained by the same method was 0% by weight per 100% by weight of the polymer.
  • Each of the powders of the polar group-containing vinylidene fluoride polymer- (1) was hot-pressed at 200 ° C. to prepare a press sheet 30 mm ⁇ 30 mm.
  • the IR spectrum of the press sheet using an infrared spectrophotometer FT-IR4100 was measured in the range of 1500cm -1 ⁇ 4000cm -1.
  • the absorbance ratio (I R ) represented by the following formula (1) was determined from the obtained IR spectrum.
  • I 10 is the apparent absorbance at a wave number of 3025 cm ⁇ 1 and I 11 is the background absorbance at a wave number of I 10
  • I 3025 I 10 ⁇ I 11 .
  • the background absorbance indicates the absorbance when the bottom of the peak on the low wavenumber side is connected to the bottom of the high wavenumber side. That is, in I 21 , a line connecting the low wavenumber side (1653 cm ⁇ 1 to 1662 cm ⁇ 1 ) and the high wavenumber side (1897 cm ⁇ 1 to 1907 cm ⁇ 1 ), which is the bottom region of absorption, is used as a baseline. The absorbance at 1750 cm ⁇ 1 is shown, and in I 11 , the straight line connecting the low wavenumber side (2859 cm ⁇ 1 to 2866 cm ⁇ 1 ) and the high wavenumber side (3306 cm ⁇ 1 to 3317 cm ⁇ 1 ) is used as the baseline. , The absorbance at 3025 cm ⁇ 1 .
  • the absorbance ratio (R) of the IR spectrum (FIG. 1) measured by the above method can be determined as follows.
  • I 20 is the apparent absorbance at a wavenumber of 1750 cm -1 is 0.24, the absorbance at a wavenumber of 1750 cm -1 when I 21 is connecting the skirt hem and 1900 cm -1 wave number 1660 cm -1 Is 0.06, and I 1750 is 0.18 from I 20 and I 21 .
  • the absorbance of the apparent I 10 is wavenumber 3025cm -1 is 0.53
  • the absorbance at a wavenumber of 3025cm -1 when I 11 is connecting the skirt hem and 3310cm -1 wavenumber 2863cm -1 is 0. 05
  • I 3025 was 0.48 from I 10 and I 11 .
  • the absorbance ratio (I R ) of the polar group-containing vinylidene fluoride polymer- (1) is 0.38.
  • the absorbance ratio (I R ) of the chlorine atom-containing vinylidene fluoride polymer- (1) was determined in the same manner.
  • the absorbance ratio (I R ) of the chlorine atom-containing vinylidene fluoride polymer- (1) was 0.07.
  • the absorbance ratio (I R ) of polyvinylidene fluoride- (1) was determined in the same manner.
  • the absorbance ratio (I R ) of polyvinylidene fluoride- (1) was 0.05.
  • the absorbance ratio (I R ) of vinylidene fluoride-hexafluoropropylene copolymer- (1) was determined in the same manner.
  • the absorbance ratio (I R ) of vinylidene fluoride-hexafluoropropylene copolymer- (1) was 0.06.
  • the absorbance ratio (I R ) of vinylidene fluoride-trifluoroethylene copolymer- (1) was determined in the same manner.
  • the absorbance ratio (I R ) of vinylidene fluoride-trifluoroethylene copolymer- (1) was 0.06.
  • Example 1 A chlorine atom-containing vinylidene fluoride polymer- (1) 2.0 g and a polar group-containing vinylidene fluoride polymer-6.0 g are uniformly dissolved in 92 g of N-methyl-2-pyrrolidone A solution was obtained.
  • the negative electrode mixture (A1) for a non-aqueous electrolyte secondary battery is dried by using a bar coater on a rolled copper foil having a thickness of 10 ⁇ m as a current collector, and the weight of the mixture layer after drying is 150 g / m 2 .
  • a negative electrode mixture (B1) for a non-aqueous electrolyte secondary battery was obtained by stirring and mixing using a product manufactured by Shinky Corporation.
  • the negative electrode mixture (B1) for a non-aqueous electrolyte secondary battery is dried by using a bar coater on a rolled copper foil having a thickness of 10 ⁇ m as a current collector, and the weight of the mixture layer after drying is 150 g / m 2 . After applying uniformly, drying at 110 ° C. in a gear oven, and heat-treating at 130 ° C., pressing is performed at 40 MPa, and the bulk density of the mixture layer is 1.7 g / cm 3 (B1) Got.
  • Example 2 A chlorine atom-containing vinylidene fluoride polymer- (1) 6.0 g and a polar group-containing vinylidene fluoride polymer- (1) 2.0 g are uniformly dissolved in 92 g of N-methyl-2-pyrrolidone, and a binder is obtained. A solution was obtained.
  • the negative electrode mixture for nonaqueous electrolyte secondary batteries (A2) is dried using a bar coater on a rolled copper foil having a thickness of 10 ⁇ m, and the weight of the mixture layer after drying is 150 g / m 2 .
  • the electrode (A2) has a bulk density of 1.7 g / cm 3 after being pressed at 40 MPa after being uniformly applied, dried at 110 ° C. in a gear oven, and heat-treated at 130 ° C. Got.
  • Example 3 4.0 g of chlorine atom-containing vinylidene fluoride polymer- (1) and 4.0 g of polar group-containing vinylidene fluoride polymer- (1) are uniformly dissolved in 92 g of N-methyl-2-pyrrolidone A solution was obtained.
  • a negative electrode mixture (A3) for a non-aqueous electrolyte secondary battery was obtained by stirring and mixing using a Shinky product.
  • the negative electrode mixture for nonaqueous electrolyte secondary batteries (A3) is dried using a bar coater on a rolled copper foil having a thickness of 10 ⁇ m, and the weight of the mixture layer after drying is 150 g / m 2 .
  • the negative electrode mixture (B5) for a non-aqueous electrolyte secondary battery is dried by using a bar coater on a rolled copper foil having a thickness of 10 ⁇ m as a current collector, and the weight of the mixture layer after drying is 150 g / m 2 .
  • the electrode is uniformly applied, dried at 110 ° C. in a gear oven, heat-treated at 130 ° C., pressed at 40 MPa, and the mixture layer has a bulk density of 1.7 g / cm 3 (B5) Got.
  • the negative electrode mixture (B6) for non-aqueous electrolyte secondary batteries is rolled onto a rolled copper foil having a thickness of 10 ⁇ m, which is a current collector, so that the weight of the mixture layer after drying becomes 150 g / m 2 .
  • the electrode is uniformly applied, dried at 110 ° C. in a gear oven, heat-treated at 130 ° C., and then pressed at 40 MPa, and the bulk density of the mixture layer is 1.7 g / cm 3 (B6) Got.
  • the negative electrode produced using the negative electrode mixture for a nonaqueous electrolyte secondary battery of the present invention is excellent in the peel strength between the mixture layer and the current collector.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery containing a chlorine atom-containing vinylidene fluoride polymer is a polar group-containing vinylidene fluoride polymer.
  • Excellent peel strength As compared with the case of using only vinyl (Comparative Example 1) and the case of using a vinylidene fluoride polymer not containing a chlorine atom instead of the chlorine atom-containing vinylidene fluoride polymer (Comparative Examples 2 to 4), Excellent peel strength.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention includes a chlorine atom-containing vinylidene fluoride polymer as an essential component, so that the negative electrode produced using the mixture includes a mixture layer, Excellent peel strength from current collector.
  • the negative electrode mixture for a non-aqueous electrolyte secondary battery of the present invention contains a polar group-containing vinylidene fluoride polymer as an essential component, so that the negative electrode manufactured using the mixture includes a mixture layer, Excellent peel strength from current collector.

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Abstract

L'invention concerne un mélange pour une électrode négative destinée à des batteries rechargeables à électrolyte non aqueux. Lorsque ce mélange est utilisé pour produire une électrode négative pour batteries rechargeables à électrolyte non aqueux, il permet d'obtenir une couche de mélange présentant une excellente résistance au pelage au niveau du collecteur de courant. Le mélange destiné à une telle électrode négative est caractérisé en ce qu'il comprend: un polymère fluorure de vinylidène présentant des groupes polaires, un polymère fluorure de vinylidène présentant des atomes de chlore, une matière active d'électrode, et un solvant organique, le polymère fluorure de vinylidène contenant les atomes de chlore contenant des atomes de chlore dans une quantité comprise entre 0,3% et 5%, par rapport à 100% dudit polymère.
PCT/JP2009/071261 2008-12-26 2009-12-21 Mélange pour produire une électrode négative destinée à une batterie rechargeable à électrolyte non aqueux, électrode négative pour batterie rechargeable à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux Ceased WO2010074041A1 (fr)

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KR1020117008500A KR101298300B1 (ko) 2008-12-26 2009-12-21 비수 전해질 2 차 전지용 부극 합제, 비수 전해질 2 차 전지용 부극 및 비수 전해질 2 차 전지
JP2010544060A JP5626791B2 (ja) 2008-12-26 2009-12-21 非水電解質二次電池用負極合剤、非水電解質二次電池用負極および非水電解質二次電池

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CN112088457B (zh) * 2018-05-31 2021-12-03 株式会社吴羽 粘接性组合物、隔离件结构体、电极结构体、非水电解质二次电池及其制造方法
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CN103155247A (zh) * 2010-10-14 2013-06-12 株式会社吴羽 非水电解质二次电池用负极混合剂、非水电解质二次电池用负极和非水电解质二次电池
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CN103155247B (zh) * 2010-10-14 2015-06-10 株式会社吴羽 非水电解质二次电池用负极混合剂、非水电解质二次电池用负极和非水电解质二次电池
CN103259039A (zh) * 2012-02-21 2013-08-21 三星Sdi株式会社 锂电池
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WO2018092677A1 (fr) * 2016-11-15 2018-05-24 株式会社クレハ Mélange d'électrode, procédé de production de mélange d'électrode, structure d'électrode, procédé de production de structure d'électrode, et batterie secondaire
JPWO2018092677A1 (ja) * 2016-11-15 2019-10-17 株式会社クレハ 電極合剤、電極合剤の製造方法、電極構造体、電極構造体の製造方法および二次電池
US11322744B2 (en) 2016-11-15 2022-05-03 Kureha Corporation Electrode mixture, method for producing electrode mixture, electrode structure, method for producing electrode structure, and secondary battery
WO2019220677A1 (fr) 2018-05-15 2019-11-21 株式会社クレハ Mélange d'électrodes, procédé de production de mélange d'électrodes, structure d'électrode, procédé de production de structure d'électrode et batterie secondaire
WO2019239781A1 (fr) * 2018-06-12 2019-12-19 株式会社クレハ Composition de liant, mélange d'électrode, structure d'électrode, procédé de fabrication de structure d'électrode et cellule secondaire
WO2020054274A1 (fr) * 2018-09-11 2020-03-19 株式会社クレハ Mélange pour électrode, procédé de production de mélange pour électrode, et procédé de production d'électrode
JPWO2020054274A1 (ja) * 2018-09-11 2021-02-15 株式会社クレハ 電極合剤、電極合剤の製造方法、および電極の製造方法

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JP5626791B2 (ja) 2014-11-19

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