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WO2024117227A1 - Particules composites pour électrode de batterie secondaire non aqueuse, leur procédé de production, électrode négative pour batterie secondaire non aqueuse et batterie secondaire non aqueuse - Google Patents

Particules composites pour électrode de batterie secondaire non aqueuse, leur procédé de production, électrode négative pour batterie secondaire non aqueuse et batterie secondaire non aqueuse Download PDF

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Publication number
WO2024117227A1
WO2024117227A1 PCT/JP2023/042958 JP2023042958W WO2024117227A1 WO 2024117227 A1 WO2024117227 A1 WO 2024117227A1 JP 2023042958 W JP2023042958 W JP 2023042958W WO 2024117227 A1 WO2024117227 A1 WO 2024117227A1
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WIPO (PCT)
Prior art keywords
secondary battery
composite particles
aqueous secondary
electrode
active material
Prior art date
Application number
PCT/JP2023/042958
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English (en)
Japanese (ja)
Inventor
慎太郎 川島
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日本ゼオン株式会社
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Publication of WO2024117227A1 publication Critical patent/WO2024117227A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

Definitions

  • the present invention relates to composite particles for non-aqueous secondary battery electrodes, a method for producing composite particles for non-aqueous secondary battery electrodes, a negative electrode for a non-aqueous secondary battery, and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries such as lithium-ion secondary batteries (hereinafter sometimes abbreviated as "secondary batteries”) are small, lightweight, have high energy density, and can be repeatedly charged and discharged, and are used for a wide range of applications.
  • Electrodes for secondary batteries have a structure in which an electrode mixture layer is disposed on an electrode substrate, the electrode mixture layer being mainly composed of an electrode active material and containing other components such as conductive materials and binders as necessary to give the electrode specific functions such as conductivity, adhesion, and flexibility.
  • Methods that have been considered for forming an electrode mixture layer include a method of forming an electrode mixture layer by applying a slurry composition containing an electrode active material, a conductive material, a binder, and a solvent onto an electrode substrate and drying the composition, and a method of forming an electrode mixture layer by pressure molding composite particles containing an electrode active material, a conductive material, a binder, and a solvent onto an electrode substrate.
  • Composite particles with various attributes that are produced by various manufacturing methods have been considered for the past (see, for example, Patent Documents 1 to 3).
  • the composite particles are required to have excellent squeegee properties (fluidity) when forming the electrode mixture layer.
  • squeegee properties fluidity
  • non-aqueous secondary batteries with electrode mixture layers that have high weight accuracy in order to achieve uniform performance in secondary batteries.
  • the above conventional composite particles leave room for improvement in terms of achieving both high levels of squeegee properties and weight accuracy of the electrode mixture layer of the secondary battery.
  • an object of the present invention is to provide composite particles for non-aqueous secondary battery electrodes, which have excellent squeegee properties and are capable of forming an electrode mixture layer with high basis weight accuracy, and a method for producing the same.
  • Another object of the present invention is to provide a negative electrode for a nonaqueous secondary battery including an electrode mixture layer with high area weight accuracy, and a nonaqueous secondary battery including the negative electrode for a nonaqueous secondary battery.
  • the present inventors have conducted extensive research with the aim of solving the above problems.
  • the inventors have discovered that composite particles in which the degree of compression, the fluidity index, and the frequency of particles with a particle size of 45 ⁇ m or less in the particle size distribution all satisfy predetermined values have excellent squeegee properties, and that the use of such composite particles can improve the weight accuracy of the electrode mixture layer, thereby completing the present invention.
  • an object of the present invention is to advantageously solve the above-mentioned problems, and the present invention relates to [1] a composite particle for a non-aqueous secondary battery electrode, which contains an electrode active material, a water-soluble polymer, and a binder, the composite particle for a non-aqueous secondary battery electrode having a degree of compression of less than 18%, a fluidity index of more than 4.0, and a frequency of particles having a particle diameter of 45 ⁇ m or less in a particle diameter distribution of less than 15 vol %.
  • the composite particles for a non-aqueous secondary battery electrode have excellent squeegee properties and can improve the weight accuracy of the electrode mixture layer.
  • the "compressibility", "fluidity index” and “frequency of particles having a particle size of 45 ⁇ m or less in the particle size distribution” can be measured using the method described in the Examples.
  • the electrode active material contains at least one of a carbon-based active material and a silicon-based active material.
  • the capacity of the secondary battery can be increased.
  • the water-soluble polymer preferably has a carboxyl group.
  • the binder is preferably a polymer containing an aliphatic conjugated diene monomer unit. If a polymer containing an aliphatic conjugated diene monomer unit is used as a binder, the electrical characteristics of the secondary battery can be further improved.
  • the present invention also aims to advantageously solve the above-mentioned problems, and the present invention is [5] a method for producing composite particles for non-aqueous secondary battery electrodes according to any one of [1] to [4] above, the method comprising a step of granulating the composite particles for non-aqueous secondary battery electrodes by a spray drying method.
  • the composite particles for a non-aqueous secondary battery electrode of the present invention can be efficiently produced by granulating the composite particles for a non-aqueous secondary battery electrode by a spray drying method.
  • Another object of the present invention is to advantageously solve the above-mentioned problems, and the present invention is [6] a method for producing composite particles for non-aqueous secondary battery electrodes according to any one of [1] to [4] above, comprising a step of granulating the composite particles for non-aqueous secondary battery electrodes by a fluidized bed granulation method.
  • the composite particles for a non-aqueous secondary battery electrode of the present invention can be efficiently produced by granulating the composite particles for a non-aqueous secondary battery electrode by a fluidized bed granulation method.
  • Another object of the present invention is to advantageously solve the above problems, and the present invention relates to [8] a negative electrode for a non-aqueous secondary battery, comprising an electrode mixture layer formed using the composite particle for a non-aqueous secondary battery electrode according to any one of [1] to [4] above.
  • the negative electrode for a nonaqueous secondary battery includes an electrode mixture layer formed using the composite particles for a nonaqueous secondary battery electrode of the present invention, and therefore has high accuracy in terms of basis weight, allowing the secondary battery to exhibit excellent electrical characteristics.
  • the present invention also aims to advantageously solve the above-mentioned problems, and the present invention relates to [9] a nonaqueous secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the negative electrode is the negative electrode for a nonaqueous secondary battery according to [8] above.
  • the nonaqueous secondary battery of the present invention has excellent electrical characteristics since it includes the negative electrode for a nonaqueous secondary battery of the present invention.
  • the present invention it is possible to provide composite particles for non-aqueous secondary battery electrodes, which have excellent squeegee properties and are capable of forming an electrode mixture layer with high basis weight accuracy, and a method for producing the same. Furthermore, according to the present invention, it is possible to provide a negative electrode for a nonaqueous secondary battery including an electrode mixture layer with high area weight accuracy, and a nonaqueous secondary battery including the negative electrode for a nonaqueous secondary battery.
  • composite particles for nonaqueous secondary battery electrodes of the present invention are not particularly limited and can be suitably used, for example, as a material for forming an electrode mixture layer provided in an electrode of a secondary battery.
  • the composite particles of the present invention can be produced, for example, by the method for producing composite particles for a non-aqueous secondary battery electrode of the present invention.
  • the negative electrode for a non-aqueous secondary battery of the present invention includes an electrode mixture layer made of the composite particles of the present invention.
  • the non-aqueous secondary battery of the present invention includes the negative electrode for a non-aqueous secondary battery of the present invention.
  • the composite particles of the present invention include an electrode active material, a water-soluble polymer, and a binder, and optionally include components such as a conductive material and an additive.
  • the composite particles of the present invention are characterized in that the degree of compression is less than 18%, the fluidity index is more than 4.0, and the frequency of particles having a particle diameter of 45 ⁇ m or less in the particle diameter distribution is less than 15 volume%.
  • the composite particles of the present invention have excellent squeegee properties because the degree of compression, the fluidity index, and the frequency of particles having a particle diameter of 45 ⁇ m or less in the particle diameter distribution each satisfy a predetermined value.
  • the composite particles for non-aqueous secondary battery electrodes of the present invention can be used in either the electrode mixture layer of the positive electrode or the negative electrode of a non-aqueous secondary battery, but are preferably used in the negative electrode.
  • the degree of compression of the composite particles must be less than 18%, and is preferably less than 14%. If the degree of compression of the composite particles is less than 18%, the aggregation of the composite particles is suppressed.
  • the degree of compression of the composite particles is preferably more than 10%, and more preferably more than 11%. If the degree of compression of the composite particles is more than 10%, the increase in the compression strain of the composite particles is suppressed, and the electrode mixture layer made of the composite particles can be suppressed from peeling off from the current collector.
  • the flowability index of the composite particles must be more than 4.0, and is preferably more than 5.0. If the flowability index of the composite particles is more than 4.0, the composite particles have good flowability and excellent squeegee properties.
  • the flowability index of the composite particles is preferably 6.0 or less. If the flowability index of the composite particles is 6.0 or less, the increase in the compression strain of the composite particles can be further suppressed, and the electrode mixture layer made of the composite particles can be further suppressed from peeling off from the current collector.
  • the composite particles must have a particle frequency of 45 ⁇ m or less in the particle size distribution of less than 15%, and preferably less than 10%. If the particle frequency of 45 ⁇ m or less in the particle size distribution of the composite particles is less than 15%, the flowability of the composite particles is further improved. In addition, the particle frequency of 45 ⁇ m or less in the particle size distribution is preferably 0.4% or more. If the particle frequency of 45 ⁇ m or less in the particle size distribution is equal to or greater than the lower limit, the increase in the compression strain of the composite particles can be further suppressed, and the electrode mixture layer made of the composite particles can be further suppressed from peeling off from the current collector.
  • the electrode active material is not particularly limited, and any known electrode active material used in secondary batteries can be used.
  • the electrode active material can usually be particles (electrode active material particles) made of a material capable of absorbing and releasing lithium ions.
  • the secondary battery is a lithium ion secondary battery
  • the present invention is not limited to the following example.
  • negative electrode active materials for lithium ion secondary batteries include carbon-based active materials, silicon-based active materials, metal-based active materials, and negative electrode active materials that are combinations of these materials.
  • the carbon-based active material refers to an active material having a carbon skeleton that can insert (or "dope") lithium.
  • Examples of the carbon-based active material include carbonaceous materials and graphite materials.
  • carbonaceous materials include graphitic carbon, whose carbon structure can be easily changed by heat treatment temperature, and non-graphitic carbon, which has a structure similar to an amorphous structure, such as glassy carbon.
  • graphitizable carbon examples include carbon materials made from tar pitch obtained from petroleum or coal. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, and pyrolytic vapor-grown carbon fiber.
  • MCMB mesocarbon microbeads
  • mesophase pitch-based carbon fiber examples include coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, and pyrolytic vapor-grown carbon fiber.
  • non-graphitizable carbon examples include phenolic resin sintered bodies, polyacrylonitrile carbon fibers, pseudo-isotropic carbon, furfuryl alcohol resin sintered bodies (PFA), and hard carbon.
  • Graphite materials include, for example, natural graphite and artificial graphite.
  • silicon-based active materials examples include silicon (Si), alloys containing silicon, SiO, SiOx, and composites of Si-containing materials and conductive carbon, which are obtained by coating or compounding Si-containing materials with conductive carbon.
  • An example of an alloy containing silicon is an alloy composition that contains silicon, aluminum, a transition metal such as iron, and further contains rare earth elements such as tin and yttrium.
  • SiOx is a compound containing at least one of SiO and SiO2 and Si, where x is usually 0.01 or more and less than 2.
  • SiOx can be formed, for example, by utilizing the disproportionation reaction of silicon monoxide (SiO).
  • SiOx can be prepared by heat treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to generate silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900°C or more, preferably 1000°C or more, in an atmosphere containing organic gas and/or steam, after pulverizing and mixing SiO and optionally a polymer.
  • the metal-based active material is an active material containing a metal, and usually refers to an active material that contains an element capable of inserting lithium in its structure and has a theoretical electric capacity per unit mass of 500 mAh/g or more when lithium is inserted.
  • the metal-based active material include lithium metal, elemental metals that can form lithium alloys (e.g., Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Sn, Sr, Zn, Ti, etc.) and their alloys, as well as oxides, sulfides, nitrides, silicides, carbides, phosphides, etc. thereof.
  • the above-mentioned negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode active material contains at least one of a carbon-based active material and a silicon-based active material.
  • the content of the electrode active material in the composite particles is preferably 90% by mass or more, and more preferably 95% by mass or more, when the total mass of the composite particles is taken as 100% by mass. If the content of the electrode active material particles in the composite particles is equal to or more than the lower limit mentioned above, the capacity of the resulting secondary battery can be further increased.
  • Water-soluble polymer together with the binder, is a component that holds the components contained in the composite particles so that they do not detach from the composite particles, and is also a component that can satisfactorily bind the electrode mixture layer formed using the composite particles to the current collector.
  • water-soluble means that when 0.5 g of the polymer is dissolved in 100 g of water at 25°C, the insoluble matter is less than 1.0 mass%.
  • the water-soluble polymer is not particularly limited, and examples thereof include cellulose-based polymers such as cellulose compounds such as carboxymethyl cellulose (CMC), carboxyethyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, and carboxyethyl methyl cellulose, and salts thereof such as ammonium salts and alkali metal salts; oxidized starch and starch phosphate; casein; various modified starches; polyethylene oxide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polysulfonic acid, polycarboxylic acid, polyacrylic acid; (meth)acrylic acid copolymers, acrylic acid-acrylamide copolymers, and other (meth)acrylamide-based polymers, and salts thereof such as ammonium salts and alkali metal salts.
  • CMC carboxymethyl cellulose
  • CMC carboxymethyl cellulose
  • ethyl cellulose ethyl cellulose
  • the water-soluble polymer is preferably a cellulose-based polymer, a (meth)acrylic acid copolymer, a (meth)acrylamide-based polymer, or a combination thereof.
  • the content of the water-soluble polymer in the composite particles is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, when the total mass of the composite particles is taken as 100% by mass. If the content of the water-soluble polymer in the composite particles is equal to or more than the above lower limit, the adhesion between the current collector and the composite particles can be further improved.
  • the binder is a component that prevents the components contained in the composite particles from being detached from the composite particles when an electrode is produced using the composite particles of the present invention, and is a component that can satisfactorily bind an electrode mixture layer made using the composite particles to a current collector.
  • the term "binder” refers to a polymer that is dispersible in an aqueous medium such as water, and such a polymer preferably exists in particulate form in the aqueous medium. That is, in the present invention, the binder is preferably a particulate binder.
  • a particulate binder usually has an insoluble content of 90% by mass or more when 0.5 g of the particulate binder is dissolved in 100 g of water at 25°C.
  • “particulate” refers to an aspect ratio of 1 or more and less than 10 as measured by a scanning electron microscope.
  • the binder is not particularly limited, and any polymer such as a conjugated diene polymer or an acrylic polymer can be used.
  • Conjugated diene polymers refer to polymers that contain conjugated diene monomer units.
  • Specific examples of conjugated diene polymers include, but are not limited to, copolymers that contain aromatic vinyl monomer units and aliphatic conjugated diene monomer units, such as styrene-butadiene copolymer (SBR), butadiene rubber (BR), acrylic rubber (NBR), and hydrogenated versions of these.
  • SBR styrene-butadiene copolymer
  • BR butadiene rubber
  • NBR acrylic rubber
  • the acrylic polymer is not particularly limited, and examples thereof include polymers containing a crosslinkable monomer unit, a (meth)acrylic acid ester monomer unit, and an acidic group-containing monomer unit.
  • (meth)acrylic means acrylic and/or methacrylic.
  • the polymer may contain monomers, such as nitrile group-containing monomer units.
  • the polymer contains an aliphatic conjugated diene monomer unit. If the binder composition contains a polymer containing an aliphatic conjugated diene monomer unit, the electrical characteristics of the secondary battery can be further improved.
  • a polymer when a polymer "contains a monomer unit”, it means that "a polymer obtained by using that monomer contains a repeating unit derived from that monomer”.
  • the content of the monomer units in the polymer can be measured by a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
  • the content of aromatic vinyl monomer units in the polymer is not particularly limited, but when the sum of all monomer units contained in the polymer is taken as 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less.
  • Aliphatic conjugated diene monomer units examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-chloro-1,3-butadiene (chloroprene), and piperylene.
  • 1,3-butadiene is preferred. These can be used alone or in combination of two or more.
  • the content of the aliphatic conjugated diene monomer units in the polymer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 10% by mass or less, and more preferably 5% by mass or less, assuming that the sum of all monomer units contained in the polymer is 100% by mass.
  • crosslinkable monomer capable of forming a crosslinkable monomer unit examples include polyfunctional ethylenically unsaturated carboxylic acid ester monomers having two or more ethylenically unsaturated bonds.
  • Bifunctional ethylenically unsaturated carboxylic acid ester monomers having two ethylenically unsaturated bonds in the molecule include allyl acrylate, allyl methacrylate, ethylene diacrylate, ethylene dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, Examples include 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol diacrylate, ethylene
  • trifunctional ethylenically unsaturated carboxylic acid ester monomers having three ethylenically unsaturated bonds in the molecule include ethoxylated isocyanuric acid triacrylate, ⁇ -caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.
  • Examples of the tetrafunctional or higher ethylenically unsaturated carboxylic acid ester monomer having four or more ethylenically unsaturated bonds in the molecule include ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, and dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.
  • the content ratio of crosslinkable monomer units in the polymer is not particularly limited and can be set appropriately.
  • (meth)acrylic acid ester monomers capable of forming the (meth)acrylic acid ester monomer units include methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl acrylate, etc. These may be used alone or in combination of two or more.
  • the content ratio of (meth)acrylic acid ester monomer units in the polymer is not particularly limited and can be set appropriately.
  • unsaturated carboxylic acid monomers capable of forming the unsaturated carboxylic acid monomer unit include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and acid anhydrides thereof, and derivatives thereof.
  • unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of derivatives of unsaturated monocarboxylic acids include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, and ⁇ -diaminoacrylic acid.
  • Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
  • Examples of acid anhydrides of unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methylmaleic anhydride, and dimethylmaleic anhydride.
  • Examples of the derivatives of unsaturated dicarboxylic acids include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, diphenyl maleate, nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, fluoroalkyl maleate, etc. These can be used alone or in combination of two or more.
  • preferred unsaturated carboxylic acid monomers are unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid.
  • the content of the acidic group-containing monomer units in the polymer is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, assuming that the sum of all monomer units contained in the polymer is 100% by mass.
  • nitrile group-containing monomers capable of forming nitrile group-containing monomer units include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group, and examples thereof include acrylonitrile; ⁇ -halogenoacrylonitriles such as ⁇ -chloroacrylonitrile and ⁇ -bromoacrylonitrile; ⁇ -alkylacrylonitriles such as methacrylonitrile and ⁇ -ethylacrylonitrile; and the like. These may be used alone or in combination of two or more.
  • the content ratio of nitrile group-containing monomer units in the polymer is not particularly limited and can be set appropriately.
  • the method for preparing the above-mentioned polymer is not particularly limited, and for example, the polymer can be prepared by polymerizing a monomer composition containing the above-mentioned monomers.
  • the content ratio of each monomer in the monomer composition used for preparing the polymer can be determined according to the content ratio of each repeating unit in the polymer.
  • the polymerization method is not particularly limited, and any method such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc.
  • any addition polymerization method such as ionic polymerization, radical polymerization, living radical polymerization, etc. can be used as the polymerization method.
  • the binder content in the composite particles is preferably 1.0% by mass or more, and more preferably 1.5% by mass or more, when the total mass of the composite particles is taken as 100% by mass. If the binder content in the composite particles is equal to or more than the above lower limit, the adhesion between the current collector and the composite particles can be further improved.
  • the composite particle of the present invention may optionally contain a conductive material.
  • the conductive material that the composite particle of the present invention may contain is intended to promote electrical contact between the electrode active materials.
  • conductive carbon materials such as carbon black (e.g., acetylene black, Ketjen Black (registered trademark), furnace black, etc.), graphite, carbon fiber, carbon flakes, etc.; fibers and foils of various metals, etc. can be used.
  • the conductive material preferably contains carbon fiber, more preferably contains ultrashort carbon fibers such as carbon nanotubes and vapor-grown carbon fibers, further preferably contains carbon nanotubes, and particularly preferably contains single-walled carbon nanotubes. These can be used alone or in combination of two or more types.
  • the content of the conductive material in the composite particles is preferably 90% by mass or more, and more preferably 95% by mass or more, when the total mass of the composite particles is taken as 100% by mass. If the content of the conductive material in the composite particles is equal to or more than the above lower limit, electrical contact between the electrode active materials can be further promoted.
  • the additives that the composite particles may contain are not particularly limited, and examples thereof include antifoaming agents, preservatives, antioxidants, reinforcing materials, leveling agents, viscosity modifiers, electrolyte additives, etc. These are not particularly limited as long as they do not affect the battery reaction, and known additives can be used. These additives can be used alone or in combination of two or more.
  • the content of the additive in the composite particles is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less, when the total mass of the composite particles is taken as 100% by mass. If the content of the additive in the composite particles is equal to or less than the above upper limit, the electrical characteristics of the secondary battery can be further improved.
  • the method for producing the composite particles of the present invention is not particularly limited, but from the viewpoint of efficiently producing the composite particles, it is preferable that the method includes a step of granulating the composite particles by a spray drying method (hereinafter referred to as "granulation step A").
  • the method for producing composite particles of the present invention preferably includes a granulation step (hereinafter referred to as "granulation step B") in which the composite particles are granulated using a fluidized bed granulation method.
  • granulation step B a granulation step in which the composite particles are granulated using a fluidized bed granulation method.
  • the method for producing composite particles of the present invention preferably includes a step of classifying the composite particles obtained as a granule (hereinafter referred to as the "classification step") after granulation step A or granulation step B.
  • the composite particles are granulated by using a spray drying method. Specifically, in the granulation step A, the slurry composition A is sprayed into hot air and dried to granulate the composite particles.
  • the slurry composition A used in the granulation step A contains at least an electrode active material, a water-soluble polymer, a binder, and a solvent, and may further contain a conductive material and an additive as necessary.
  • the electrode active material, the water-soluble polymer, the binder, the conductive material, and the additive the electrode active material, the water-soluble polymer, the binder, the conductive material, and the additive described in the above section "Composite particles for non-aqueous secondary battery electrode of the present invention" can be used.
  • the solvent used in the slurry composition A is not particularly limited, and either water or an organic solvent can be used.
  • the organic solvent that can be used include acetonitrile, N-methyl-2-pyrrolidone, tetrahydrofuran, acetone, acetylpyridine, cyclopentanone, dimethylformamide, dimethylsulfoxide, methylformamide, methyl ethyl ketone, furfural, ethylenediamine, dimethylbenzene (xylene), methylbenzene (toluene), cyclopentyl methyl ether, and isopropyl alcohol.
  • water it is preferable to use water.
  • These solvents may be used alone or in combination of two or more at any desired mixing ratio.
  • the method for preparing the slurry composition A is not particularly limited, and the slurry composition A can be prepared, for example, by adding the above-mentioned electrode active material, water-soluble polymer, binder, solvent, and conductive material and additives used as necessary to a solvent and mixing them.
  • the granulation step A preferably includes a kneading step.
  • the granulation step A preferably includes, for example, a kneading step of mixing an electrode active material, a water-soluble polymer, and an optional conductive material and additives, and a preparation step of adding a binder to the mixture obtained through the kneading step and further mixing to prepare the slurry composition A.
  • the term "thick kneading" means mixing the components in a state in which the solid content is higher than that of the slurry composition A finally obtained.
  • the solids concentration in the kneading process is preferably 60% by mass or more, more preferably 65% by mass or more, and even more preferably 70% by mass or more.
  • the solids concentration of the final slurry composition A is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more.
  • the hot air temperature during spray drying is preferably 25 to 250°C, more preferably 50 to 220°C, and further preferably 80 to 200°C.
  • the method of blowing hot air is not particularly limited, and examples thereof include a method in which the hot air and the spray direction flow horizontally in parallel, a method in which the droplets are sprayed at the top of the drying tower and then descend together with the hot air, a method in which the sprayed droplets come into countercurrent contact with the hot air, and a method in which the sprayed droplets first flow in parallel with the hot air and then fall by gravity to come into countercurrent contact with the hot air.
  • the temperature of the slurry composition A to be sprayed is not limited, and may be room temperature or may be heated to a temperature higher than room temperature.
  • Spray drying can be carried out using a known spray dryer.
  • the device used to spray the slurry composition A is not particularly limited, and examples include atomizers.
  • Examples of atomizers include devices using a rotating disk system, a cup system, a two-fluid nozzle system, and a pressurized system.
  • the composite particles are granulated using a fluidized bed granulation method.
  • the slurry composition B is sprayed from a spray or the like onto the electrode active material fluidized by hot air to perform aggregation granulation, thereby granulating the composite particles.
  • the slurry composition B used in the granulation step B contains at least a water-soluble polymer, a binder, and a solvent, and may further contain a conductive material and an additive as necessary.
  • a water-soluble polymer, binder, conductive material, and additive the water-soluble polymer, binder, conductive material, and additive described in the above section "Composite particles for non-aqueous secondary battery electrode of the present invention" can be used.
  • the solvent the same solvent as that used in the above-mentioned slurry composition A can be used.
  • the method for preparing the slurry composition B is not particularly limited, and for example, the slurry composition B can be prepared by adding the above-mentioned water-soluble polymer, binder, solvent, and the conductive material and additives used as necessary to a solvent and mixing them.
  • the solid content concentration of the slurry composition B is preferably 40% by mass or more, and more preferably 50% by mass or more. If the solid content concentration of the slurry composition B is equal to or more than the above lower limit, the components contained in the slurry composition B can be uniformly dispersed.
  • the electrode active material to be fluidized As the electrode active material to be fluidized, the electrode active material described above in the section "Composite particles for non-aqueous secondary battery electrodes of the present invention" can be used.
  • the method for fluidizing the electrode active material is not particularly limited, and the electrode active material may be fluidized by any known method.
  • the temperature of the hot air used to fluidize the electrode active material is preferably 80°C or higher, and more preferably 100°C or higher.
  • the classification step the composite particles obtained through the granulation step A or the granulation step B are further classified.
  • the classification method is not particularly limited, but may be a dry classification method such as gravity classification, inertial classification, and centrifugal classification; a wet classification method such as sedimentation classification, mechanical classification, and hydraulic classification; or a sieve classification method using a sieve net such as a vibrating sieve or an in-plane motion sieve. Among these, the sieve classification method is preferred.
  • a sieve classification method By performing the classification step, composite particles that can further improve the weight accuracy of the electrode mixture layer can be produced.
  • the negative electrode for a non-aqueous secondary battery of the present invention (hereinafter, also simply referred to as "negative electrode”) includes an electrode mixture layer.
  • the electrode mixture layer is made of the composite particles for a non-aqueous secondary battery electrode of the present invention described above. Therefore, the negative electrode of the present invention has excellent appearance because molding defects such as variations in basis weight in the electrode mixture layer are suppressed, and the electrical characteristics of the secondary battery can be improved.
  • the electrode mixture layer is provided, for example, on a current collector provided on the electrode.
  • the electrode of the present invention may have an electrode mixture layer on only one side of the current collector, or may have an electrode mixture layer on both sides.
  • the negative electrode of the present invention may have layers other than the electrode mixture layer and the current collector (hereinafter simply referred to as "other layers") on the surface of the negative electrode (particularly the surface on the electrode mixture layer side).
  • the electrode mixture layer is formed using the composite particles of the present invention. That is, the electrode mixture layer contains the above-mentioned electrode active material, water-soluble polymer, and binder, and may optionally contain the above-mentioned conductive material and additives.
  • the components contained in the electrode mixture layer are those contained in the composite particles of the present invention described above, and the preferred ratios and attributes of the components in the electrode mixture layer are the same as the preferred ratios and attributes of the components in the composite particles.
  • a material having electrical conductivity and electrochemical durability can be selected and used according to the type of secondary battery.
  • a current collector made of iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, etc. can be used as the current collector of the negative electrode for a lithium ion secondary battery.
  • copper foil is particularly preferable as the current collector used for the negative electrode.
  • the above-mentioned materials may be used alone or in combination of two or more kinds in any ratio.
  • the negative electrode of the present invention having an electrode mixture layer made of the above-mentioned composite particles is not particularly limited, and can be manufactured, for example, by forming the above-mentioned composite particles of the present invention into a sheet shape and then laminating it on a current collector. From the viewpoint of further increasing the productivity of the secondary battery, a method of directly pressure-molding the composite particles on the current collector is preferable.
  • Examples of the pressure molding method include a roll pressure molding method in which a roll pressure molding device equipped with a pair of rolls is used, and while a current collector is being fed by the rolls, composite particles are fed to the roll pressure molding device by a feeder such as a screw feeder to mold an electrode mixture layer on the current collector, and a method in which composite particles are spread on a current collector, the composite particles are smoothed by a blade or the like to adjust the thickness, and then molded by a pressure device.
  • the roll pressure molding method is preferred.
  • Non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolyte, and a separator, and the negative electrode is the above-mentioned negative electrode for a non-aqueous secondary battery of the present invention. Therefore, the secondary battery of the present invention has excellent electrical characteristics.
  • the nonaqueous secondary battery is a lithium ion secondary battery will be described as an example, but the present invention is not limited to the following example.
  • the positive electrode is not particularly limited, and a known positive electrode can be used.
  • the positive electrode can be a positive electrode obtained by forming a positive electrode mixture layer on a current collector using a known method.
  • the negative electrode As the negative electrode, the above-mentioned negative electrode for secondary batteries of the present invention is used.
  • an organic electrolyte in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used.
  • the lithium salt for example, LiPF6 , LiAsF6 , LiBF4 , LiSbF6 , LiAlCl4 , LiClO4 , CF3SO3Li, C4F9SO3Li , CF3COOLi , ( CF3CO ) 2NLi , ( CF3SO2 ) 2NLi , ( C2F5SO2 )NLi, etc. are listed.
  • LiPF6 LiClO4 , and CF3SO3Li are preferred, and LiPF6 is particularly preferred, because they are easily dissolved in the solvent and show a high degree of dissociation .
  • the electrolyte may be used alone or in combination of two or more kinds in any ratio.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but examples of suitable organic solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; and the like. A mixture of these solvents may also be used. The concentration of the electrolyte in the electrolytic solution can be appropriately adjusted.
  • the electrolytic solution may contain known additives such as vinylene carbonate, fluoroethylene carbonate, and ethyl methyl sulfone.
  • the separator is not particularly limited, and for example, those described in JP 2012-204303 A can be used. Among these, a microporous film made of a polyolefin resin (polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferred, since it can reduce the thickness of the entire separator, thereby increasing the ratio of the electrode active material in the secondary battery and increasing the capacity per volume.
  • a polyolefin resin polyethylene, polypropylene, polybutene, polyvinyl chloride
  • the lithium ion secondary battery according to the present invention can be produced, for example, by stacking a positive electrode and a negative electrode with a separator therebetween, wrapping or folding the stack according to the battery shape as necessary, placing the stack in a battery container, injecting an electrolyte into the battery container, and sealing the container.
  • a fuse In order to prevent the occurrence of an internal pressure rise in the secondary battery, overcharging and overdischarging, etc., a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary.
  • the shape of the secondary battery may be, for example, any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, etc.
  • the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
  • “%” and “parts” expressing amounts are based on mass unless otherwise specified.
  • the ratio of a monomer unit formed by polymerizing a certain monomer in the polymer usually coincides with the ratio (feed ratio) of the certain monomer to the total monomers used in the polymerization of the polymer, unless otherwise specified.
  • the degree of compression, loose bulk density, packed bulk density, fluidity index, frequency of particles having a particle diameter of 45 ⁇ m or less in the particle size distribution, squeegee property (fluidity), cohesiveness, 2 ⁇ fluctuation ratio to the target basis weight value, and basis weight stability were measured and evaluated using the following methods.
  • N/C (1/ab) + (1/a)N
  • the horizontal axis is "tapping count N”
  • the loose bulk density and packed bulk density obtained above were plotted, and a straight line expressed by the Kawakita formula was obtained by the least squares method. The slope (1/a) of the obtained straight line was then calculated, and this slope was defined as the fluidity index (1/a).
  • ⁇ Frequency of particles with a particle size of 45 ⁇ m or less in particle size distribution The volumetric particle size distribution of the composite particles was measured by a dry integral particle size distribution measurement using a laser diffraction/scattering particle size distribution measurement device (Microtrac Bell, "MT3200II") with the pressure of the dispersion air during measurement set to 0.05 MPa.
  • the volumetric frequency of composite particles with a particle size of 45 ⁇ m or less was calculated from the integral particle size distribution measured using a laser diffraction/scattering particle size distribution measurement device (Microtrac Bell, "MT3200II"). The obtained frequency was taken as the particle frequency of particles with a particle size of 45 ⁇ m or less in the particle size distribution.
  • ⁇ Squeegee property (fluidity)> The composite particles were filled into a container made of SUS (Steel Use Stainless) with a powder cover, and tapped 180 times using a powder tester device (manufactured by Hosokawa Micron Corporation, "PT-S"). After that, the powder cover was removed, and the composite particles that exceeded the volume of the container were squeegeeed using a manual squeegee, and the composite particles after squeegeeing were observed.
  • the squeegeeability (fluidity) of the composite particles was evaluated according to the following criteria.
  • A The surface of the composite particle after squeegeeing is even with no irregularities.
  • B After squeegeeing, minute irregularities are generated on the surface of the composite particle, and the surface is not uniform.
  • C After squeegeeing, large irregularities are generated from the surface to the inside of the composite particle, and the surface is not uniform.
  • the composite particles were taken out of the SUS container, and the appearance of the composite particles was observed.
  • the aggregation property of the composite particles was evaluated according to the following criteria. Note that the "re-tapping" in the following criteria was performed by taking the composite particles out of the SUS container, observing them, and then putting the composite particles back into the SUS container and tapping them 180 times in the same manner as in the evaluation method of the squeegee property (fluidity) described above.
  • A When taken out of the SUS container, the composite particles do not form agglomerates.
  • ⁇ 2 ⁇ fluctuation ratio to target basis weight> The composite particles were aligned on a copper foil having a thickness of 10 ⁇ m by a doctor blade. The aligned composite particles were then roll-pressed to obtain a negative electrode sample (electrode width: 80 mm, electrode length: 0.5 m). At this time, the roll gap was adjusted so that the target weight was 12.00 ⁇ 0.25 mg/ cm2 , and the sample was pressed under the following conditions. Conveyor speed: 1 m/min Roll press load: 3.5 MPa Press temperature: 50°C The obtained sample was punched out at 12 places with a size of 20 mm ⁇ , and the basis weight (mg/cm 2 ) was measured.
  • the above procedure was repeated 12 times to determine the average weight per unit area (Ave).
  • the fluctuation ratio with respect to the target basis weight was used to evaluate according to the following criteria: The smaller the 2 ⁇ fluctuation ratio with respect to the target basis weight, the more excellent the basis weight stability of the composite particles.
  • Example 1 Preparation of Slurry Composition>
  • 94.5 parts of artificial graphite as a carbon-based active material 3.0 parts of SiOx as a silicon-based active material
  • 0.5 parts of a 1% aqueous solution of carboxymethylcellulose sodium salt (CMC-Na) in terms of solid content as a water-soluble polymer 0.5 parts of a 4% aqueous solution of sodium polyacrylate (PAA-Na) in terms of solid content were added as negative electrode active materials.
  • CMC-Na carboxymethylcellulose sodium salt
  • PAA-Na sodium polyacrylate
  • aqueous dispersion containing a styrene-butadiene-methacrylic acid copolymer (SBR, manufactured by Zeon Corporation, product name "BM-451B”) as a binder was added to the mixture in terms of solid content, and ion-exchanged water was added to adjust the final solid content concentration to 50%, and the mixture was further mixed for 10 minutes (preparation step). Then, the mixture was degassed under reduced pressure to obtain a slurry composition for a lithium ion secondary battery negative electrode.
  • SBR styrene-butadiene-methacrylic acid copolymer
  • Atomizer Rotating disk type (diameter: 50 mm) Rotational speed: 25,000 rpm Hot air temperature (outlet temperature): 180°C
  • the obtained composite particles (1) were used to measure and evaluate the degree of compression, loose bulk density, packed bulk density, fluidity index, frequency of particles with a particle diameter of 45 ⁇ m or less in the particle diameter distribution, squeegee property (fluidity), cohesiveness, 2 ⁇ fluctuation value relative to the target basis weight, and basis weight stability. The results are shown in Table 1.
  • Example 2 The composite particles (1) obtained in Example 1 were classified using two types of sieves with nominal openings of 75 ⁇ m and 45 ⁇ m (JIS Z8801-1) (classification step). Then, composite particles (2) having a particle diameter of more than 45 ⁇ m and not more than 75 ⁇ m were obtained. Except for using the composite particle (2) instead of the composite particle (1), the measurement and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 The composite particles (1) obtained in Example 1 were classified using two types of sieves with nominal openings of 106 ⁇ m and 75 ⁇ m (JIS Z8801-1) (classification step). Then, composite particles (3) having a particle diameter of more than 75 ⁇ m and not more than 106 ⁇ m were obtained. Except for using the composite particle (3) instead of the composite particle (1), the measurement and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Preparation of Slurry Composition> A slurry composition was prepared without performing a kneading process. Specifically, 94.5 parts of artificial graphite as a carbon-based active material, 3.0 parts of SiOx as a silicon-based active material, 0.5 parts of a 1% aqueous solution of carboxymethylcellulose sodium salt (CMC-Na) in solid content equivalent, and 0.5 parts of a 4% aqueous solution of sodium polyacrylate (PAA-Na) in solid content equivalent were added to a planetary mixer with a disperser as the negative electrode active material.
  • CMC-Na carboxymethylcellulose sodium salt
  • PAA-Na sodium polyacrylate
  • the obtained composite particles were classified using two types of sieves with notional openings of 75 ⁇ m and 45 ⁇ m (JIS Z8801-1) (classification step) to obtain composite particles (4) having a particle diameter of more than 45 ⁇ m and not more than 75 ⁇ m. Except for using the composite particle (4) instead of the composite particle (1), the measurement and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 The composite particles granulated in Example 4 were classified using two types of sieves with nominal openings of 106 ⁇ m and 75 ⁇ m (JIS Z8801-1) (classification step) to obtain composite particles (5) having a particle size of more than 75 ⁇ m and not more than 106 ⁇ m. Except for using the composite particle (5) instead of the composite particle (1), the measurement and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • a slurry composition was prepared without performing a kneading process. Specifically, 94.5 parts of artificial graphite as a carbon-based active material, 3.0 parts of SiOx as a silicon-based active material, 0.5 parts of a 1% aqueous solution of carboxymethylcellulose sodium salt (CMC-Na) in solid content equivalent, and 0.5 parts of a 4% aqueous solution of sodium polyacrylate (PAA-Na) in solid content equivalent were added to a planetary mixer with a disperser as the negative electrode active material.
  • CMC-Na carboxymethylcellulose sodium salt
  • PAA-Na sodium polyacrylate
  • Example 2 ⁇ Preparation of Slurry Composition>
  • the composite particles (1) obtained in Example 1 were classified using a sieve with a notional mesh size of 45 ⁇ m (JIS Z8801-1) (classification step), and composite particles (7) having a particle size of 45 ⁇ m or less were obtained. Except for using the composite particle (7) instead of the composite particle (1), the measurement and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • CMC carboxymethylcellulose sodium salt
  • PAA sodium polyacrylate
  • the present invention it is possible to provide composite particles for non-aqueous secondary battery electrodes, which have excellent squeegee properties and are capable of forming an electrode mixture layer with high basis weight accuracy, and a method for producing the same. Furthermore, according to the present invention, it is possible to provide a negative electrode for a nonaqueous secondary battery including an electrode mixture layer with high area weight accuracy, and a nonaqueous secondary battery including the negative electrode for a nonaqueous secondary battery.

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Abstract

Le but de la présente invention est de proposer des particules composites pour une électrode de batterie secondaire non aqueuse qui possèdent d'excellentes propriétés de raclette et qui permettent de former une couche de mélange d'électrode avec une précision élevée de grammage. Les particules composites pour une électrode de batterie secondaire non aqueuse selon la présente invention comprennent un matériau actif d'électrode, un polymère soluble dans l'eau et un liant, la compressibilité étant inférieure à 18 %, l'indice de fluidité étant supérieur à 4,0, et, dans une distribution granulométrique, la fréquence de particules possédant une taille de particule inférieure ou égale à 45 µm étant inférieure à 15 % en volume.
PCT/JP2023/042958 2022-11-30 2023-11-30 Particules composites pour électrode de batterie secondaire non aqueuse, leur procédé de production, électrode négative pour batterie secondaire non aqueuse et batterie secondaire non aqueuse WO2024117227A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251965A (ja) * 2007-03-30 2008-10-16 Nippon Zeon Co Ltd 電気化学素子用電極およびその製造方法
WO2013129571A1 (fr) * 2012-02-29 2013-09-06 日本ゼオン株式会社 Particules composites pour électrode d'élément électrochimique ainsi que leur procédé de fabrication, et électrode d'élément électrochimique ainsi que matériau de celle-ci
JP2015118821A (ja) * 2013-12-19 2015-06-25 トヨタ自動車株式会社 非水電解質二次電池電極用シートの製造方法および非水電解質二次電池の製造方法
WO2016013434A1 (fr) * 2014-07-22 2016-01-28 日本ゼオン株式会社 Particules composites pour électrode d'élément électrochimique, électrode d'élément électrochimique, élément électrochimique, procédé de fabrication de particules composites pour électrode d'élément électrochimique, et procédé de fabrication d'électrode d'élément électrochimique
JP2016091904A (ja) * 2014-11-07 2016-05-23 日立化成株式会社 リチウムイオン二次電池用負極材の製造方法、リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008251965A (ja) * 2007-03-30 2008-10-16 Nippon Zeon Co Ltd 電気化学素子用電極およびその製造方法
WO2013129571A1 (fr) * 2012-02-29 2013-09-06 日本ゼオン株式会社 Particules composites pour électrode d'élément électrochimique ainsi que leur procédé de fabrication, et électrode d'élément électrochimique ainsi que matériau de celle-ci
JP2015118821A (ja) * 2013-12-19 2015-06-25 トヨタ自動車株式会社 非水電解質二次電池電極用シートの製造方法および非水電解質二次電池の製造方法
WO2016013434A1 (fr) * 2014-07-22 2016-01-28 日本ゼオン株式会社 Particules composites pour électrode d'élément électrochimique, électrode d'élément électrochimique, élément électrochimique, procédé de fabrication de particules composites pour électrode d'élément électrochimique, et procédé de fabrication d'électrode d'élément électrochimique
JP2016091904A (ja) * 2014-11-07 2016-05-23 日立化成株式会社 リチウムイオン二次電池用負極材の製造方法、リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池

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