WO2019073820A1 - Composition d'agent de dispersion pour bouillie de batterie secondaire, et application de celle-ci - Google Patents

Composition d'agent de dispersion pour bouillie de batterie secondaire, et application de celle-ci Download PDF

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Publication number
WO2019073820A1
WO2019073820A1 PCT/JP2018/036267 JP2018036267W WO2019073820A1 WO 2019073820 A1 WO2019073820 A1 WO 2019073820A1 JP 2018036267 W JP2018036267 W JP 2018036267W WO 2019073820 A1 WO2019073820 A1 WO 2019073820A1
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Prior art keywords
component
weight
secondary battery
parts
composition
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Ceased
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PCT/JP2018/036267
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English (en)
Japanese (ja)
Inventor
貴之 青木
浩史 小田
中村　佳介
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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Priority to JP2019548122A priority Critical patent/JP6676225B2/ja
Publication of WO2019073820A1 publication Critical patent/WO2019073820A1/fr
Anticipated expiration legal-status Critical
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a dispersant composition for secondary battery slurry and its use. More specifically, a dispersant composition for a secondary battery slurry having good slurry dispersion stability, a coating property, a secondary battery slurry composition having a good film drying property, and two having excellent heat resistance and liquid retention property.
  • the present invention relates to a coating for a secondary battery and a method of manufacturing the same.
  • capacitors such as a lithium ion secondary battery, a nickel hydrogen secondary battery, a secondary battery such as a nickel cadmium secondary battery, an electric double layer capacitor, and the like, which can be repeatedly used by charging, are used in electronic devices.
  • Secondary batteries are being rapidly developed as batteries for use in portable electronic devices, hybrid vehicles, and the like.
  • a lithium ion secondary battery is mainly composed of a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution, and various studies have been made to improve battery characteristics.
  • the positive electrode is manufactured by applying and drying a positive electrode secondary battery slurry containing a positive electrode active material and a solvent on a current collector.
  • the negative electrode is manufactured by applying and drying a negative electrode secondary battery slurry containing a negative electrode active material and a solvent on a current collector.
  • the separator is a material capable of isolating the positive electrode and the negative electrode to improve the safety of the battery, and for example, a porous polyolefin film has excellent properties.
  • separators coated with a secondary battery slurry for a separator further containing organic particles or inorganic particles on the surface of a separator substrate such as a porous film of polyolefin are also developed and dried.
  • a secondary battery material capable of further improving the safety.
  • a method of providing a shutdown function of preventing further heat generation by blocking passage of ions between the positive and negative electrodes by the above-mentioned separator at the time of abnormal heat generation In the shutdown function, the separator is melted and made non-porous at the time of abnormal heat generation, and the passage of ions can be blocked to suppress further heat generation.
  • a separator made of a porous film made of polyolefin suppresses further heat generation by shutting down (passing) the passage of ions by melting and non-performing at about 80 to 180 ° C. during abnormal heat generation of the battery. .
  • the positive electrode and the negative electrode may come in direct contact with each other due to shrinkage, film breakage or the like in the separator made of the porous film to cause a short circuit.
  • the separator made of the porous film made of polyolefin has insufficient shape stability and may not suppress abnormal heat generation due to a short circuit.
  • Patent Document 1 a heat-resistant layer containing a filler of fine particles and a porous film mainly composed of polyolefin as a base material (hereinafter sometimes referred to as "base material porous film”) are laminated.
  • a separator for a non-aqueous electrolyte secondary battery comprising a laminated porous film;
  • Patent Document 2 is a method of using a fine particle filler whose surface is modified as a heat-resistant layer of the separator;
  • Patent Document 3 is characterized by the chemical structure of a binder resin The method etc. of making it hold and bind a filler is disclosed.
  • the object of the present invention is to provide a dispersant composition for secondary battery slurry having good dispersion stability, a secondary battery slurry composition having good coatability and film drying property, and good coatability and film drying property. It is an object of the present invention to provide a method for producing a secondary battery slurry composition and a battery using the secondary battery slurry composition.
  • the dispersant composition for a secondary battery slurry of the present invention is a dispersant composition containing the following component (B), the following component (C) and the following component (D),
  • the weight ratio of the component (C) to the component (B) is 0.5 to 3.5,
  • the content of the component (D) is 0.1 to 500 parts by weight, and the glass of the component (B)
  • the transition point is Tg (B) (° C.)
  • the glass transition point of the component (C) is Tg (C) (° C.), and the following formula (I) is satisfied.
  • the component (D) is 0.1 to 500 parts by weight, and the component (A) is
  • the glass transition point of) is Tg (A) (° C)
  • the glass transition point of the component (B) is Tg (B) (° C)
  • the glass transition point of the component (C) is Tg (C) (° C) It is preferable to satisfy the following formula (II).
  • Component (A) Water-insoluble polymer particle component A essentially containing an alkyl ester group-containing monomer unit (II) and containing 0% by weight or more and less than 31% by weight of a carboxyl group-containing monomer unit (I)
  • Tg (A) is ⁇ 100 to 50 (° C.).
  • the component (A) further contains a nitrogen-containing monomer unit (III), and the monomer unit (II) is 100 parts by weight, the monomer unit (III) is 0.1 to 200 It is preferable that it is a weight part. It is preferable that the 4% by weight aqueous solution viscosity at 20 ° C. of the component (C) is 1 to 500 mPa ⁇ s.
  • a dispersant composition for a secondary battery slurry comprising a combination of at least two agents, wherein the combination essentially comprises a first agent containing the component (A), the component (B) and the component It is preferable to include a second agent which essentially contains (C).
  • the viscosity of the 1% by weight aqueous solution of carboxymethyl cellulose is preferably 1 to 100 mPa ⁇ s at 20 ° C.
  • the secondary battery slurry composition of the present invention is a secondary battery slurry composition containing the following component (B), the following component (C), the following component (D), and inorganic particles,
  • the content of the inorganic particles is 100 parts by weight
  • the content of each of the components (A) is 0.1 to 50 parts by weight
  • the component (B) is 0.1 to 50 parts by weight
  • the component (C) is 0.1 to 50 parts by weight
  • the component (D) is 0.001 to 20 parts by weight.
  • the method for producing a material for a secondary battery of the present invention comprises mixing the dispersant composition obtained by mixing the following component (B), the following component (C) and the following component (D) with a solvent, and mixing the dispersant Step (a) of obtaining a solution, step (b) of mixing the dispersant mixed solution and the inorganic particles to obtain a slurry composition, current collector of positive electrode, current collector of negative electrode, positive electrode, negative electrode, separator The step (c) of forming a film by applying the above-mentioned slurry composition to at least one selected from and drying it.
  • the positive electrode for a secondary battery according to the present invention is a positive electrode for a secondary battery having a film for the positive electrode on a current collector, and the film is formed of the non-volatile component of the slurry composition of the secondary battery.
  • the negative electrode for a secondary battery of the present invention is a negative electrode for a secondary battery having a film for the negative electrode on a current collector, and the film is formed of the non-volatile component of the slurry composition of the secondary battery.
  • the separator for a secondary battery of the present invention is a separator having a film for a separator, and the film is formed of the non-volatile component of the slurry composition for a secondary battery.
  • the secondary battery of the present invention is a secondary battery including a negative electrode, a positive electrode, a separator, and an electrolytic solution, wherein at least one of the negative electrode, the positive electrode and the separator is a non-volatile component of the secondary battery slurry composition. And a coating formed by
  • the slurry containing the dispersant composition for a secondary battery slurry of the present invention has good dispersion stability.
  • the secondary battery slurry composition of the present invention is excellent in coating properties and drying properties of the film.
  • a film for a secondary battery produced using the secondary battery slurry composition of the present invention is excellent in heat resistance and liquid retention.
  • the dispersant composition for a secondary battery slurry of the present invention essentially comprises the components (B) to (D). It is preferable to further include the component (A) because the dispersion stability is improved.
  • each component which comprises the dispersing agent composition for secondary battery slurries is demonstrated in detail.
  • Component (A) is a non-water-soluble polymer particle component A which essentially contains an alkyl ester group-containing monomer unit (II) and contains 0 to less than 31% by weight of a carboxyl group-containing monomer unit (I) .
  • Component (A) contains 0 to less than 31% by weight of carboxyl group-containing monomer unit (I), but from the viewpoint of dispersion stability, 0.1 to 30% by weight is more preferable, and 0.5 to 20% by weight. % Is more preferred, 1 to 10% by weight is particularly preferred, and 2 to 5% by weight is most preferred. If it is 31% by weight or more, the dispersion stability may be deteriorated.
  • carboxyl group-containing monomer unit (I) a non-substituted (free) carboxyl group which is copolymerizable with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and is not esterified is used. It is not particularly limited as long as it is a monomer having one or more.
  • a carboxyl group-containing monomer (I) for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer, ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomer, and ⁇ And ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers.
  • the carboxyl group-containing monomers also include monomers in which the carboxyl groups of these monomers form a carboxylate.
  • an anhydride of an ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid can also be used as a carboxyl group-containing monomer because the acid anhydride group is cleaved after copolymerization to form a carboxyl group.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid and cinnamic acid.
  • Examples of the ⁇ , ⁇ -unsaturated polyvalent carboxylic acid monomer include butenedioic acid such as fumaric acid and maleic acid, itaconic acid and citraconic acid.
  • anhydride of the ⁇ , ⁇ -unsaturated polyvalent carboxylic acid maleic anhydride, itaconic anhydride and the like can be mentioned.
  • alkyl ester group-containing monomer unit (II) methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl
  • Acrylic acid alkyl esters such as acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, cetyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl Methacrylate, heptyl methacrylate, octyl methacrylate, 2-eth
  • acrylic acid alkyl ester is preferable, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate are more preferable, and ethyl acrylate is particularly preferable.
  • the component (A) further contains the nitrogen-containing monomer unit (III) from the viewpoint of coatability.
  • the nitrogen-containing monomer unit (III) for example, acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, fumaronitrile, acrylamide, methacrylamide, methylene bis acrylamide, N-methylol acrylamide, isopropyl acrylamide, diethyl Acrylamide etc. are mentioned.
  • the monomer unit (I) is preferably 0 to 100 parts by weight from the viewpoint of dispersion stability, The amount is more preferably 0.1 to 30 parts by weight, still more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, and most preferably 2 to 5 parts by weight. If it exceeds 100 parts by weight, the dispersion stability may deteriorate.
  • the monomer unit (III) is 0.1 to 200 parts by weight
  • the amount is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, particularly preferably 1 to 10 parts by weight, and most preferably 2 to 5 parts by weight. If the amount is less than 0.1 parts by weight, the coatability may be deteriorated. If it exceeds 200 parts by weight, the dispersion stability may deteriorate.
  • the solubility of the component (A) in water is non-water soluble because of its excellent coatability.
  • the solubility of the component (A) in water at 25 ° C. is not particularly limited, but preferably 10 g / 1000 ml or less, more preferably 5 g / 1000 ml or less, further preferably 1 g / 1000 ml or less, particularly preferably It is 0.5 g / 1000 ml or less, most preferably 0.1 g / 1000 ml or less. If the solubility of the component (A) in water is more than 10 g / 1000 ml, the binding properties of the secondary battery slurry may not be sufficient.
  • the preferable lower limit of the solubility of the component (A) in water is 0 g / 1000 ml.
  • the 20% aqueous dispersion viscosity at 25 ° C. of the component (A) is preferably 0.1 to 1000 mPa ⁇ s, more preferably 1 to 500 mPa ⁇ s, from the viewpoint of dispersion stability and coatability.
  • the viscosity is more preferably 2 to 1400 mPa ⁇ s, particularly preferably 3 to 300 mPa ⁇ s, and most preferably 4 to 200 mPa ⁇ s. If it is less than 0.1 mPa ⁇ s, dispersion stability may be deteriorated.
  • the weight reduction at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas, and heating at 40 ° C. to a temperature rise of 10 ° C./min) of the component (A) is not particularly limited, but preferably 20 % By weight or less, more preferably 15% by weight or less, still more preferably 10% by weight or less, particularly preferably 5% by weight or less, most preferably 3% by weight or less.
  • the weight loss at 300 ° C. by thermogravimetry of polymer particles is more than 20% by weight, the binding property may not be sufficient.
  • the zeta potential of a 5% by weight aqueous dispersion at a measurement temperature of 25 ° C. is preferably 0 to -100 mV, more preferably -10 to -90 mV, still more preferably -20 to -80 mV, particularly preferably -30 to -70 mV , Most preferably -35 to -65 mV.
  • the handling property may not be excellent.
  • the component (A) may be in the form of a polymer particle emulsion in which polymer particles are dispersed in water.
  • concentration of the polymer particles in the case of the polymer particle emulsion is not particularly limited, but preferably 1 to 80% by weight, more preferably 10 to 70% by weight, still more preferably 15 to 60% by weight, particularly Preferably it is 20 to 50% by weight, most preferably 30 to 50% by weight.
  • the concentration of the polymer particles in the case of the polymer particle emulsion is less than 1% by weight, the dispersibility may not be excellent.
  • the concentration of the polymer particles is more than 80% by weight, the handling property may not be excellent.
  • the average particle size of the component (A) is not particularly limited, but preferably 0.001 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m, particularly preferably 0.05 to 1 ⁇ m, and most preferably 0.1 to It is 0.8 ⁇ m.
  • the average particle diameter of the component (A) is less than 0.001 ⁇ m, the production may be difficult and it may not be preferable.
  • the average particle diameter of the component (A) is more than 100 ⁇ m, the dispersion stability may be deteriorated, which may not be preferable.
  • the weight average molecular weight of the component (A) is not particularly limited, but, for example, usually 100,000 or more and less than 3,000,000, preferably 250,000 or more and less than 2,000,000, more preferably 500,000 or more and less than 1.8 million, more preferably 750,000 or more and less than 1.6 million, particularly preferably 350,000 or more and less than 1.5 million. If the weight average molecular weight of the component (A) is less than 100,000, the binding property may not be excellent. On the other hand, if the weight average molecular weight of the component (A) is 3,000,000 or more, the handling property may not be excellent.
  • Component (B) is a water-soluble polymer component B containing 70% by weight or more of the nitrogen-containing monomer unit (III).
  • the nitrogen-containing monomer unit (III) the same as those described above for the component (A) can be mentioned.
  • acrylamide, methacrylamide, methylene bis acrylamide, N-methylol acrylamide, isopropyl acrylamide and diethyl acrylamide are particularly preferable from the viewpoint of exhibiting the effect of the present invention.
  • the component (B) contains 70% by weight or more of the nitrogen-containing monomer unit (III), preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and 100% by weight Particularly preferred. If it is less than 70% by weight, dispersibility is insufficient.
  • the solubility of the component (B) in water is water-soluble because of its excellent dispersibility.
  • the viscosity of a 20% aqueous solution at 25 ° C. of the component (B) is preferably 2000 to 20000 mPa ⁇ s, more preferably 5000 to 19000 mPa ⁇ s, and preferably 10000 to 18000 mPa, from the viewpoint of dispersion stability and coatability. S is more preferable, 11,000 to 17000 mPa ⁇ s is particularly preferable, and 12000 to 16000 mPa ⁇ s is most preferable. If it is less than 2000 mPa ⁇ s, dispersion stability may be deteriorated.
  • the weight average molecular weight of the component (B) is not particularly limited, but, for example, usually 100,000 or more and less than 3,000,000, preferably 250,000 or more and less than 2,000,000, more preferably 500,000 or more and less than 1.8 million, more preferably 750,000 or more and less than 1.6 million, particularly preferably 350,000 or more and less than 1.5 million. If the weight average molecular weight of the component (B) is less than 100,000, the binding property may not be excellent. On the other hand, when the weight average molecular weight of the said component (B) is 3 million or more, it may not be excellent in handling property.
  • the weight loss at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas, and heating at 40 ° C. to a temperature rise of 10 ° C./min) of the component (B) is not particularly limited, but preferably 0 It is -50 wt%, more preferably 1-40 wt%, still more preferably 2-30 wt%, particularly preferably 3-20 wt%, most preferably 5-15 wt%. If the weight loss at 300 ° C. by thermogravimetry of the component (B) is more than 50% by weight, the heat resistance may not be sufficient.
  • Component (C) contains 60 to 99% by weight of at least one selected from carboxyl group-containing monomer (I) and hydroxy group-containing monomer unit (IV), and has a degree of polymerization of 100 to 10000.
  • Polymer component C As a carboxyl group-containing monomer (I), the same thing as what was already described by the said component (A) is mentioned.
  • the hydroxy group-containing monomer unit (IV) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, vinyl alcohol, etc. Good.
  • vinyl alcohol is particularly preferable from the viewpoint of exhibiting the effect of the present invention.
  • the monomer unit of the vinyl alcohol may be obtained by hydrolyzing polyvinyl acetate obtained by polymerizing vinyl acetate.
  • Component (C) contains 60 to 99% by weight, preferably 70 to 99% by weight, of at least one selected from carboxyl group-containing monomer (I) and hydroxy group-containing monomer unit (IV). -95 wt% is more preferred, 83-93 is particularly preferred, 85-90 wt% is particularly preferred, and 87-89 wt% is most preferred. If it is less than 60% by weight, dispersibility is insufficient. If it exceeds 99% by weight, the coatability is insufficient.
  • component (C) of the present invention for example, Aquaric series (polyacrylic acid, Nippon Catalyst Co., Ltd.), Kurare Popbar series (polyvinyl alcohol, Kuraray Co., Ltd.), Denkapovar series (polyvinyl alcohol, Denka Co., Ltd.) ), J-POVAL series (polyvinyl alcohol, Nippon Shokubai Bi-Poval Co., Ltd.), Cellol series (polyvinyl alcohol, Sekisui Chemical Co., Ltd.) and other commercially available water-soluble polymers may be used. .
  • Aquaric series polyacrylic acid, Nippon Catalyst Co., Ltd.
  • Kurare Popbar series polyvinyl alcohol, Kuraray Co., Ltd.
  • Denkapovar series polyvinyl alcohol, Denka Co., Ltd.
  • J-POVAL series polyvinyl alcohol, Nippon Shokubai Bi-Poval Co., Ltd.
  • Cellol series polyvinyl alcohol
  • the solubility of the component (C) in water is water-soluble because of its excellent dispersibility.
  • the 4% aqueous solution viscosity at 25 ° C. of the component (C) is preferably 1 to 500 mPa ⁇ s, more preferably 5 to 300 mPa ⁇ s, and further preferably 10 to 200 mPa ⁇ s from the viewpoint of dispersion stability and coatability. More preferably, it is s, 20 to 150 mPa ⁇ s is particularly preferable, and 30 to 100 mPa ⁇ s is most preferable. If it is less than 1 mPa ⁇ s, dispersion stability may be deteriorated. If it exceeds 500 mPa ⁇ s, the coatability may be deteriorated.
  • the weight-average molecular weight of the component (C) is not particularly limited, but, for example, usually 10, 000 to less than 5,000,000, preferably 10,000 to less than 1.5 million, more preferably 15,000 to less than 1,000,000 More preferably, it is 20,000 or more and less than 500,000, particularly preferably 50,000 or more and less than 250,000, and most preferably 60000 or more and less than 150,000.
  • the weight average molecular weight of the component (C) is less than 10,000, the binding property may not be excellent.
  • the weight average molecular weight of the said component (B) is 500 or more, it may not be excellent in handling property.
  • the degree of polymerization of the component (C) is not particularly limited, but is, for example, usually 100 or more and less than 10000, preferably 300 or more and less than 5000, more preferably 500 or more and less than 3000, still more preferably 1000 or more and less than 2500, particularly preferably Is 1500 or more and less than 2000. If the degree of polymerization of the component (C) is less than 100, the binding property may not be excellent. On the other hand, when the polymerization degree of the said component (B) is 10000 or more, it may not be excellent in handling property.
  • the weight loss at 300 ° C. by thermogravimetry (TGA, introduction of dry air as a purge gas and heating at 40 ° C. to a temperature rise of 10 ° C./min) of the component (C) is not particularly limited, but preferably 0 It is -50 wt%, more preferably 1-40 wt%, still more preferably 2-30 wt%, particularly preferably 3-20 wt%, most preferably 5-15 wt%. If the weight loss at 300 ° C. by thermogravimetry of the component (C) is more than 50% by weight, the heat resistance may not be sufficient.
  • Component (A), component (B) and component (C) may contain other monomer units.
  • the other monomer unit is not particularly limited, but, for example, styrene-based monomers such as styrene, ⁇ -methylstyrene, chlorostyrene, etc .; glycidyl (meth) acrylate, hydroxymethyl acrylate glycidyl ether, 2-hydroxyethyl Glycidyl group-containing monomer units such as acrylate glycidyl ether, 3-hydroxypropyl acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, glycidyl vinyl ether, glycidyl allyl ether, diglycidyl ether, epichlorohydrin, glycidyl trimethyl ammonium chloride and the like; Maleimide monomers such as N-phenyl maleimide, N- (2-chlorophenyl) maleimi
  • Component (A), component (B) and component (C) are polymers comprising a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds together with the polymerizable monomer It may be.
  • the crosslinking agent is not particularly limited.
  • aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) (Meth) acrylate compounds such as acrylate, glycerin di (meth) acrylate and pentaerythritol tetra (meth) acrylate; carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexyl carbodiimide, polycarbodiimide and the like System compounds; polyfunctional epoxy compounds; oxazoline compounds; polyfunctional hydrazide compounds; isocyanate compounds; melanin compounds; urea compounds etc., and one or more may be used in combination.
  • aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene
  • Tg (A) (° C) of the component (A) As a glass transition point Tg (A) (° C) of the component (A), -100 to 50 (° C) is preferable, -80 to 25 ° C is more preferable, -60 to 10 ° C is more preferable, -40 to 0 C. is particularly preferred. Below -100 ° C., dispersibility may be insufficient, and above 50 ° C., film formation may be insufficient.
  • the glass transition point Tg (B) (° C.) of the component (B) is not particularly limited, but is preferably 50 to 250 (° C.), more preferably 80 to 200 ° C., still more preferably 100 to 180 ° C. ⁇ 160 ° C. is particularly preferred. Below 50 ° C., dispersibility may be insufficient, and above 250 ° C., film formation may be insufficient.
  • the glass transition point Tg (C) (° C.) of the component (C) is not particularly limited, but is preferably 0 to 250 (° C.), more preferably 10 to 200 ° C., further preferably 25 to 150 ° C. -100 ° C. is particularly preferred. Below 0 ° C., dispersibility may be insufficient, and above 250 ° C., film formation may be insufficient.
  • Formula (II) is more preferably 50 ⁇ (Tg (B) + Tg (C)) / 2-Tg (A) ⁇ 180, 60 ⁇ (Tg (B) + Tg (C)) / 2-Tg (A) ⁇ 160 is more preferable, and 80 ⁇ (Tg (B) + Tg (C)) / 2 ⁇ Tg (A) ⁇ 150 is particularly preferable.
  • Tg (A) (° C.), Tg (B) (° C.), and Tg (C) (° C.) do not satisfy the above formula (II), the film formation may be insufficient.
  • the solubility parameter SP (A) (cal / cm 3 ) 1/2 of the component (A) is usually 8 to 13 (cal / cm 3 ) 1/2 or 8.5 to 12.5 (cal / cm 3 ) 1/2 is preferable, 9 to 12 (cal / cm 3 ) 1/2 is more preferable, 9.5 to 11.5 (cal / cm 3 ) 1/2 is more preferable, and 10 to 11 (cal / cm 3) ) 1/2 is particularly preferred. If the SP (A) is less than 8, the dispersibility may be insufficient, and if it is more than 13, the film formation may be insufficient.
  • the solubility parameter SP (B) (cal / cm 3 ) 1/2 of the component (B) is usually 10 to 18 (cal / cm 3 ) 1/2 , 11 to 17.5 (cal / cm 3 ) 1 / 2 is preferable, 12 to 17 (cal / cm 3 ) 1/2 is more preferable, 13 to 16.5 (cal / cm 3 ) 1/2 is more preferable, and 14 to 16 (cal / cm 3 ) 1/2 Is particularly preferred. If the SP (B) is less than 10, the dispersibility may be insufficient, and if it is more than 18, the film formation may be insufficient.
  • the solubility parameter SP (C) (cal / cm 3 ) 1/2 of the component (C) is usually 10 to 18 (cal / cm 3 ) 1/2 , 11 to 17.5 (cal / cm 3 ) 1 / 2 is preferable, 12 to 17 (cal / cm 3 ) 1/2 is more preferable, 13 to 16.5 (cal / cm 3 ) 1/2 is more preferable, and 14 to 16 (cal / cm 3 ) 1/2 Is particularly preferred. If SP (C) is less than 10, dispersibility may be insufficient, and if it is more than 18, film formation may be insufficient.
  • the solubility parameter of the component (A) is SP (A) (cal / cm 3 ) 1/2
  • the solubility parameter of the component (B) is SP (B) (cal / cm 3 ) 1/2
  • the component (C) When the solubility parameter of (1) is SP (C) (cal / cm 3 ) 1/2 , it is preferable to satisfy the following formula (III).
  • Formula (III) is usually 2 ⁇ (SP (B) + SP (C)) / 2-SP (A) ⁇ 10, 2.5 ⁇ (SP (B) + SP (C)) / 2-SP (A) ⁇ 9 is preferable, 3 ⁇ (SP (B) + SP (C)) / 2-SP (A) ⁇ 8 is more preferable, 3.5 ⁇ (SP (B) + SP (C)) / 2-SP (A) ) ⁇ 7 is more preferable, and 4 ⁇ (SP (B) + SP (C)) / 2-SP (A) ⁇ 6 is particularly preferable.
  • the formula (III) is 2 or less, the dispersibility is insufficient, and when it is 10 or more, the film formability is insufficient.
  • the solubility parameter in the present invention is determined by the molecular attraction constant method.
  • the degree of swelling SW (A) (fold) of the component (A) with respect to the electrolytic solution is not particularly limited, but is, for example, 2 to 10 times, preferably 2.5 to 9 times, more preferably More than 3 times and less than 8 times, more preferably more than 3.5 times and less than 7 times, particularly preferably more than 4 times and less than 6 times. If the swelling degree SW (A) of the component (A) with respect to the electrolyte solution is less than 2, the flexibility may not be excellent. On the other hand, if the swelling degree SW (A) of the component (A) with respect to the electrolyte solution is 10 times or more, the binding property may not be excellent.
  • the swelling degree SW (B) (fold) of the component (B) with respect to the electrolytic solution is not particularly limited, but for example, 1 to 5 times, preferably 1.1 to 4 times, more preferably It is 1.2 times or more and less than 3.5 times, more preferably 1.3 times or more and less than 3 times, particularly preferably 1.4 times or more and less than 2.5 times.
  • the swelling degree SW (B) of the component (B) with respect to the electrolytic solution is less than 1, the dispersibility is not excellent.
  • the swelling degree SW (B) of the component (B) with respect to the electrolyte solution is 5 or more, the handling property may not be excellent.
  • the degree of swelling SW (C) (fold) of the component (C) with respect to the electrolytic solution is not particularly limited, but for example, 1 to 5 times, preferably 1.1 to 4 times, more preferably It is 1.2 times or more and less than 3.5 times, more preferably 1.3 times or more and less than 3 times, particularly preferably 1.4 times or more and less than 2.5 times.
  • the swelling degree SW (C) of the component (C) with respect to the electrolytic solution is less than 1, the dispersibility is not excellent.
  • the swelling degree SW (C) of the component (C) with respect to the electrolyte solution is 5 or more, the handling property may not be excellent.
  • the swelling degree of the component (A) is SW (A) (twice), the swelling degree of the component (B) is SW (B) (twice), and the swelling degree of the component (C) is SW (C) (twice)
  • Formula (IV) is usually 0.01 ⁇ (SW (B) + SW (C)) / (SW (A) ⁇ 2) ⁇ 0.99, 0.05 ⁇ (SW (B) + SW (C)) / (SW (A) x 2) ⁇ 0.8 is preferable, 0.1 ⁇ (SW (B) + SW (C)) / (SW (A) x 2) ⁇ 0.7 is more preferable, 0.2 ⁇ (SW (B) + SW (C)) / (SW (A) x 2) ⁇ 0.6 is more preferable, 0.3 ⁇ (SW (B) + SW (C)) / (
  • the electrolyte used for measuring the degree of swelling is not particularly limited, and examples thereof include alkyl carbonate compounds such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate, etc. Two or more types may be sufficient.
  • the weight ratio of the component (C) to the component (B) is from 0.5 to 3.5, preferably from 0.6 to 2, from the viewpoint of dispersion stability and coatability. It is more preferably 1.5, still more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1. If it is less than 0.5, the dispersion stability is deteriorated. When it exceeds 3.5, dispersion stability deteriorates.
  • the component (A) is 100 parts by weight
  • the component (B) is usually 1 to 3000 parts by weight, preferably 10 to 2000 parts by weight, and preferably 25 to 1500, from the viewpoint of dispersion stability and coatability.
  • the component (A) is 100 parts by weight
  • the component (C) is usually 1 to 3000 parts by weight, preferably 10 to 2000 parts by weight, and preferably 25 to 1500, from the viewpoint of dispersion stability and coatability. It is more preferable that it is part by weight, more preferably 50 to 1000 parts by weight, particularly preferably 75 to 500 parts by weight, and most preferably 100 to 300 parts by weight. If it is less than 1 part by weight, dispersion stability may be deteriorated. If it exceeds 2000 parts by weight, the coatability may be deteriorated.
  • the dispersant composition of the present invention essentially comprises the surfactant component D which is the component (D).
  • the surfactant component D plays a role in improving the dispersion stability and the coatability of the slurry.
  • the surfactant component D includes anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • anionic surfactant examples include fatty acid salts such as sodium oleate; alkyl sulfuric acid ester salts such as sodium lauryl sulfate; polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; Alkyl benzene sulfonates such as sodium sulfonate; alkane sulfonates; polyoxyalkylene alkyl ether sulfates; higher fatty acid amide sulfonates such as stearoyl methyl taurine Na; N-acyl sarcosine salts such as sodium lauroyl sarcosine; monostearyl phosphate Alkyl phosphates such as sodium acid sodium; polyoxyalkylene alkyl ether phosphoric acid ester salts such as polyoxyethylene oleyl ether sodium phosphate; dioctyl sulfocoha Long-chain sulfosuccinates such
  • an alkyl trimethyl ammonium salt As said cationic surfactant, an alkyl trimethyl ammonium salt; a dialkyl dimethyl ammonium salt; an alkylamine salt etc. are mentioned, for example, You may use together 1 type or 2 types or more.
  • non-ionic surfactant examples include polyoxyalkylene oxide adduct alkyl ether such as POE (30) lauryl ether; polyoxyalkylene styrenated phenyl ether such as polyoxyethylene (24) styrenated phenyl ether; sorbitan mono An ester compound of a polyhydric alcohol such as palmitate and a monovalent fatty acid; a polyoxyalkylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether; a polyoxyalkylene fatty acid ester such as polyoxyethylene monolaurate; a polyoxyalkylene sorbitan fatty acid Glycerine fatty acid ester; polyoxyalkylene castor oil; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid ester; Phosphorus fatty acid esters, alkyl glycerol ether; polyoxyalkylene cholesteryl ether; alkylpolyl
  • the POE indicates polyoxyethylene
  • the POP indicates polyoxypropylene
  • the POE (12) indicates 12 mol addition of polyoxyethylene.
  • the amphoteric surfactant include imidazoline type amphoteric surfactant; betaine type amphoteric surfactant; amino acid type amphoteric surfactant and the like, and one type or two or more types may be used in combination.
  • the content of the component (D) is not particularly limited, but when the total content of the component (B) and the component (C) is 100 parts by weight, it is generally 0.01 to 500 parts by weight, preferably It is 0.1 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, particularly preferably 1 to 10 parts by weight, and most preferably 2 to 5 parts by weight. When the content of the component (D) is less than 0.01 parts by weight, the dispersibility and the coatability are not sufficient. On the other hand, when the content of the component (D) is more than 500 parts by weight, the handling property is not excellent.
  • the content of the component (D) is not particularly limited, but generally 0.01 to 500 when the total content of the component (A), the component (B) and the component (C) is 100 parts by weight. Parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, particularly preferably 1 to 10 parts by weight, most preferably 2 to 5 parts by weight. When the content of the component (D) is less than 0.01 parts by weight, the dispersibility and the coatability are not sufficient. On the other hand, when the content of the component (D) is more than 500 parts by weight, the handling property is not excellent.
  • the dispersant composition for a secondary battery slurry of the present invention preferably contains an antifoam component (E) from the viewpoint of improving the handling property of the secondary battery slurry and the coating property.
  • an antifoam component (E) from the viewpoint of improving the handling property of the secondary battery slurry and the coating property.
  • said component (E) since it is excellent in antifoaming property as it is at least 1 sort (s) or more selected from a polysiloxane type antifoamer and a silica fine powder, it is preferable.
  • the content of the component (E) is not particularly limited, but when the total content of the component (A), the component (B) and the component (C) is 100 parts by weight, it is usually 0.0001 to 10 Parts by weight, preferably 0.0005 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, particularly preferably 0.005 to 0.1 parts by weight, most preferably 0.01 to 0.05 parts by weight It is a department.
  • the content of the antifoaming agent is less than 0.0001 parts by weight, the defoaming properties may not be sufficient.
  • the content of the antifoaming agent is more than 10 parts by weight, the coating properties may not be excellent.
  • the dispersant composition for a secondary battery slurry of the present invention may contain other components other than the components described above.
  • the other components are not particularly limited, and examples thereof include dispersion aids, pH adjuster components, and rheology adjusters.
  • the pH adjuster used in the present invention may be included for the purpose of enhancing the dispersion stability.
  • the pH adjuster is not particularly limited, but is preferably at least one or more selected from an alkali (earth) metal hydroxide, ammonium, and an inorganic acid, for example, because of excellent versatility.
  • the alkali (earth) metal refers to an alkali metal or an alkaline earth metal.
  • the content of the pH adjuster is not particularly limited, but generally 0.01 to 10 parts by weight when the total content of the components (A), (B) and (C) is 100 parts by weight. It is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, particularly preferably 0.5 to 3 parts by weight, and most preferably 1 to 2 parts by weight.
  • the content of the pH adjuster is less than 0.01 parts by weight, the dispersion stability may not be sufficient.
  • the content of the pH adjuster is more than 10 parts by weight, the coating properties may not be excellent.
  • the rheology modifier used in the present invention may be included for the purpose of enhancing the dispersion stability and the coating property.
  • the rheology modifier is appropriately selected and is not particularly limited.
  • Inorganic thickeners can be mentioned.
  • carboxymethylcellulose is preferable because the rheology modifier is excellent in dispersibility.
  • the degree of etherification of carboxymethyl cellulose is not particularly limited from the viewpoint of excellent dispersibility, but is usually 0.55 to 1.1, preferably 0.6 to 1, and more preferably 0.65 to 0.9, Particularly preferably, it is 0.65 to 0.8, and most preferably 0.7 to 0.75.
  • the viscosity of the 1% by weight aqueous solution of carboxymethyl cellulose at 20 ° C. is not particularly limited, but is usually 1 to 100 mPa ⁇ s, preferably 3 to 50, more preferably 5 to 20, and particularly preferably 6 to 15, Most preferably, it is 7-13.
  • the content of the carboxymethyl cellulose is not particularly limited, but is usually 1 to 500 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the total content of the components (B) and (C). Parts, more preferably 25 to 150 parts by weight, particularly preferably 40 to 100 parts by weight, and most preferably 50 to 70 parts by weight.
  • the content of the carboxymethylcellulose is less than 1 part by weight, the dispersibility and the coatability may not be sufficient.
  • the content of the carboxymethylcellulose is more than 500 parts by weight, the handling property is not excellent.
  • Dispersant composition for secondary battery slurry, method and form of production thereof The method for producing the dispersant composition for a secondary battery slurry is not particularly limited, and component (A): water-insoluble polymer particle component A, component (B): water-soluble polymer component B, component (C): The method etc. of mixing the water-soluble polymer component C, component (D): surfactant component D etc. can be mentioned.
  • the effective concentration of the dispersant composition for secondary battery slurry is not particularly limited as to the surface tension at 25 ° C. of a 0.1 wt% aqueous solution, but preferably 20 to 50 mN / m, more preferably 25 to 45 mN / m. Particularly preferably 25 to 40 mN / m, most preferably 25 to 35 mN / m. If it is less than 20 mN / m, the drying property may not be excellent. If it exceeds 50 mN / m, the coating properties may be poor.
  • the dispersant composition for a secondary battery slurry measures the foaming power by the Los Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C., which will be described in detail in the following examples.
  • the foaming force immediately after the flow of the dispersant composition for a slurry is 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, still more preferably 20 mm or less, particularly preferably 10 mm or less.
  • the foaming force immediately after the falling 5 minutes after 25 minutes is 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, particularly preferably 5 mm or less.
  • the coatability of the slurry for secondary batteries is not enough that the foaming force immediately after flow-down is more than 50 mm by a Los Miles test method. Moreover, the coating property of the slurry for secondary batteries is not enough in the foaming force of 5 minutes after immediately after flowing-down being more than 25 mm.
  • the zeta potential at a measurement temperature of 25 ° C. of the dispersant composition for a secondary battery slurry is not particularly limited, but is preferably -20 to -100 mV, more preferably -25 to -80 mV, particularly preferably -30 to- 70 mV, most preferably -35 to -60 mV. If it is less than -100 mV, the handling may be bad. If it exceeds -20 mV, the dispersibility may not be excellent.
  • the pH of the dispersant composition for a secondary battery slurry is not particularly limited, but is preferably 4.0 to 12.0, more preferably 5.0 to 11.0, and particularly preferably 6.0 to 10. 0, most preferably 7.0 to 9.0.
  • the pH is less than 4.0, the coatability may be poor.
  • it is over 12.0, the handling property may be bad.
  • the contact angle of the dispersant composition for a secondary battery slurry after 1,600 msec after the droplets of the dispersant composition are dropped on the surface of the polyolefin resin preferably 10 to 60 °, More preferably, it is 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. Below 10 °, dispersibility may not be excellent. If it exceeds 60 °, the coatability may be poor.
  • the contact angle after 1,600 msec after dropping the droplets of the dispersant composition for secondary battery slurry on the surface of the inorganic oxide plate of the dispersant composition for secondary battery slurry is preferably The angle is 10 to 60 °, more preferably 15 to 60 °, particularly preferably 20 to 50 °, and most preferably 30 to 40 °. Below 10 °, dispersibility may not be excellent. If it exceeds 60 °, the coatability may be poor.
  • the raw material of the inorganic oxide plate used for the contact angle measurement is not particularly limited, but silica (silicon oxide), alumina such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, etc. (aluminum oxide), etc. Can be mentioned.
  • the non-volatile content concentration of the dispersant composition for secondary battery slurry is usually 1 to 90%, preferably 10 to 80%, more preferably 20 to 70%, particularly preferably 30 to 60%, most preferably 35-55%. If it is less than 1%, the dispersibility may not be excellent. If it exceeds 90%, the stability may be bad.
  • the dispersant composition for a secondary battery slurry may be a composition composed of a combination of at least two agents.
  • the combination is a first agent essentially containing the component (A) and a second agent essentially containing the component (B) and the component (C)
  • the handling is performed. It is preferable because it has excellent properties.
  • the first agent essentially contains the component (A) and contains the component (D), the component (E), other components and water other than the component (B) and the component (C) More preferable.
  • the second agent essentially contains the component (B) and the component (C) and contains the component (D), the component (E), the other component and water other than the component (A) More preferable.
  • the secondary battery slurry composition of the present invention is obtained by a production method in which inorganic particles are dispersed in a solvent in the presence of the above-described dispersant composition for a secondary battery slurry.
  • the method for producing the secondary battery slurry composition of the present invention is not particularly limited. For example, a dispersant adjustment step of mixing the dispersant composition for a secondary battery slurry and a solvent, and the dispersant adjustment step
  • the manufacturing method etc. which include the inorganic particle dispersion process which disperse
  • the inorganic particles will be described later because they differ depending on the application of the secondary battery slurry composition.
  • the content of the component (A) in the secondary battery slurry composition is not particularly limited, but is 0.1 to 50 parts by weight, preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the inorganic particles. More preferably, it is 1 to 5 parts by weight, still more preferably 2 to 10 parts by weight, and particularly preferably 3 to 5 parts by weight. If it exceeds 50 parts by weight, the battery performance is not excellent. On the other hand, when the amount is less than 0.1 parts by weight, the coatability may not be sufficient.
  • the content of the component (B) in the secondary battery slurry composition is not particularly limited, but is 0.1 to 50 parts by weight, preferably 0.3 to 10 parts by weight, with respect to 100 parts by weight of the inorganic particles.
  • the amount is more preferably 0.5 to 5 parts by weight, still more preferably 0.7 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight. If it exceeds 50 parts by weight, the battery performance is not excellent. On the other hand, if the amount is less than 0.1 parts by weight, the coatability is not sufficient.
  • the content of the component (C) in the secondary battery slurry composition is not particularly limited, but is 0.1 to 50 parts by weight, preferably 0.3 to 10 parts by weight, with respect to 100 parts by weight of the inorganic particles.
  • the amount is more preferably 0.5 to 5 parts by weight, still more preferably 0.7 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight. If it exceeds 50 parts by weight, the battery performance is not excellent. On the other hand, if the amount is less than 0.1 parts by weight, the coatability is not sufficient.
  • the content of the other components in the secondary battery slurry composition is not particularly limited and can be used.
  • the content of a rheology modifier such as carboxymethyl cellulose is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the inorganic particles. It is 0.3 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and particularly preferably 0.7 to 2 parts by weight. If it exceeds 50 parts by weight, the battery performance is not excellent. On the other hand, if the amount is less than 0.1 parts by weight, the coatability is not sufficient.
  • the secondary battery slurry composition measures the foaming power by the Los Miles test method under the measurement conditions of a concentration of 0.1% by weight and a temperature of 25 ° C. which will be described in detail in the following examples.
  • the foaming force immediately after the flow-down is 50 mm or less, preferably 40 mm or less, more preferably 30 mm or less, still more preferably 20 mm or less, particularly preferably 10 mm or less.
  • the foaming force immediately after the falling 5 minutes after 25 minutes is 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, particularly preferably 5 mm or less.
  • the coating property is not sufficient.
  • the foaming force after 5 minutes immediately after the flow is more than 25 mm, the coating property is not sufficient.
  • the pH of the secondary battery slurry composition is not particularly limited, but is preferably 4.0 to 12.0, more preferably 5.0 to 11.0, particularly preferably 6.0 to 10.0, Preferably, it is 7.0 to 9.0.
  • the pH is less than 4.0, the coatability may be poor.
  • it is over 12.0, the handling property may be bad.
  • the solvent for dispersing the inorganic particles is not particularly limited, and may be an organic solvent or water, but water is preferable because of its low cost and low risk of harmfulness.
  • the water contained in the secondary battery slurry composition of the present invention may be any of tap water, ion exchanged water, distilled water and the like.
  • the content of the solvent in the secondary battery slurry composition is not particularly limited, but is, for example, 1 to 10000 parts by weight, preferably 10 to 1000 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of inorganic particles.
  • the amount is 500 parts by weight, more preferably 60 to 300 parts by weight, particularly preferably 80 to 200 parts by weight, and most preferably 100 to 150 parts by weight. If the content of the solvent in the secondary battery slurry composition is more than 10000 parts by weight with respect to 100 parts by weight of the inorganic particles, the battery performance may not be excellent. On the other hand, when the content of the solvent in the secondary battery slurry composition is less than 1 part by weight with respect to 100 parts by weight of the inorganic particles, the coatability may not be sufficient.
  • the secondary battery slurry composition of the present invention includes, in addition to the components described above, a hydrotrope agent, a protective colloid agent, an antibacterial agent, an antifungal agent, a colorant, an antioxidant, a deodorant, a crosslinking agent, and a catalyst. , And may further contain an emulsion stabilizer, a chelating agent and the like.
  • the application of the secondary battery slurry composition of the present invention is not particularly limited, and examples thereof include the application to the positive electrode, the application to the negative electrode, and the surface coating application such as the positive electrode, the negative electrode and the separator.
  • the application to the positive electrode the application to the negative electrode
  • the surface coating application such as the positive electrode, the negative electrode and the separator.
  • the secondary battery slurry composition of the present invention can be used as a secondary battery positive electrode application.
  • a positive electrode active material, a conductive support agent, etc. are mentioned.
  • the secondary battery slurry composition for secondary battery positive electrode application can be normally applied to a current collector sheet, dried and thinned to be used as a positive electrode for secondary battery.
  • the positive electrode active material is not particularly limited.
  • the conductive aid is not particularly limited, but, for example, carbon black such as furnace black, acetylene black and ketjen black; graphene; carbon nanotubes such as carbon nanofibers, single-walled carbon nanotubes and multi-walled carbon nanotubes; A composite metal fine particle etc. are mentioned, 1 type, or 2 or more types may be sufficient.
  • the current collector of the positive electrode is not particularly limited as long as it is a material having electron conductivity and capable of supplying a current to the positive electrode material.
  • the secondary battery slurry composition of the present invention can be used as a secondary battery negative electrode application.
  • a negative electrode active material As an inorganic particle of the slurry composition for secondary battery negative electrodes in case the secondary battery slurry composition is used as a secondary battery negative electrode application, a negative electrode active material, a conductive support agent, etc. are mentioned.
  • the secondary battery slurry composition for secondary battery negative electrode application can be generally applied to a current collector sheet, dried and thinned to be used as a negative electrode for secondary battery.
  • the negative electrode active material is not particularly limited.
  • natural graphite, artificial graphite, expanded graphite, activated carbon, carbon fiber, coke, soft carbon, hard carbon, and other carbon materials Silicon such as Si; SiO, SnO, Metal oxides such as SnO 2 , CuO, Li 4 Ti 5 O 12 ; Si-Al, Al-Zn, Si-Mg, Al-Ge, Si-Ge, Si-Ag, Zn-Sn, Ge-Ag, Alloys such as Ge-Sn, Ge-Sb, Ag-Sn, Ag-Ge, Sn-Sb, etc .; tin phosphate glass, etc. may be mentioned, and one or more kinds may be used.
  • the conductive aid is not particularly limited, but, for example, carbon black such as furnace black, acetylene black and ketjen black; graphene; carbon nanotubes such as carbon nanofibers, single-walled carbon nanotubes and multi-walled carbon nanotubes; A composite metal fine particle etc. are mentioned, 1 type, or 2 or more types may be sufficient.
  • the current collector of the negative electrode may be any material as long as it has electron conductivity and can conduct electricity to the negative electrode material, and is not particularly limited.
  • the secondary battery slurry composition of the present invention can be used as a surface coating application of a separator, and also as a surface coating application of a positive electrode or a negative electrode described above.
  • Non-conductive particles and the like can be mentioned as inorganic particles of the secondary battery slurry composition when the secondary battery slurry composition is used for surface coating.
  • Non-conductive particles are not particularly limited, but, for example, alumina (aluminum oxide) such as silica (silicon oxide), ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, etc., titania (titanium oxide), magnesia (Magnesium oxide), zirconia (zirconium oxide), calcium oxide, barium oxide, tin oxide, strontium oxide, niobium oxide, cerium oxide, tungsten oxide, indium oxide, gallium oxide, yttrium oxide, iron oxide, antimony oxide, white carbon, etc.
  • alumina aluminum oxide
  • silica silicon oxide
  • ⁇ -alumina ⁇ -alumina
  • ⁇ -alumina ⁇ -alumina
  • ⁇ -alumina etc.
  • titania titanium oxide
  • magnesia magnesia
  • zirconia zirconium oxide
  • calcium oxide barium oxide, tin oxide, strontium oxide, niobium
  • the average particle size of the nonconductive particles is not particularly limited, but is usually 0.001 to 100 ⁇ m, preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 1 ⁇ m, and particularly preferably 0.1 to 0.8 ⁇ m. And most preferably 0.2 to 0.7 ⁇ m.
  • the average particle size of the nonconductive particles is less than 0.001 ⁇ m, the production may be difficult, which may not be preferable.
  • the average particle size of the nonconductive particles is more than 100 ⁇ m, the dispersibility may be deteriorated, which is not preferable.
  • the BET specific surface area of the non-conductive particles is not particularly limited, but is, for example, usually 0.1 to 30 m 2 / g, preferably 1 to 18 m 2 / g, more preferably 4 to 14 m 2 / g, particularly preferably Is 5 to 10 m 2 / g, most preferably 8 to 10 m 2 / g.
  • the BET specific surface area of the non-conductive particles is less than 0.1 m 2 / g, the film-forming property may be deteriorated, which may not be preferable.
  • the BET specific surface area of the nonconductive particles is more than 30 m 2 / g, the handling property may be deteriorated, which is not preferable.
  • the electric conductivity of the non-conductive particles is not particularly limited, but is preferably 100 ⁇ S / cm or less, more preferably 80 ⁇ S / cm or less, particularly preferably 40 ⁇ S / cm or less, and most preferably 20 ⁇ S / cm or less. is there. If the electrical conductivity of the nonconductive particles is more than 100 ⁇ S / cm, the battery performance may be deteriorated, which is not preferable.
  • the zeta potential of the secondary battery slurry composition for use in surface coating is not particularly limited, but the zeta potential of a 5% by weight aqueous dispersion at a measurement temperature of 25 ° C. is preferably -10 to -100 mV, more preferably It is ⁇ 10 to ⁇ 90 mV, more preferably ⁇ 20 to ⁇ 80 mV, particularly preferably ⁇ 30 to ⁇ 70 mV, and most preferably ⁇ 35 to ⁇ 65 mV.
  • the handling property may not be excellent.
  • the zeta potential of the secondary battery slurry composition for surface coating application at a concentration of 5% by weight is more than ⁇ 10 mV, dispersibility may not be sufficient.
  • the case where the secondary battery slurry composition of the present invention is used as a surface coating application of a secondary battery separator will be described in detail.
  • a separator is usually used to prevent a short circuit between the positive electrode and the negative electrode.
  • the separator's hole is blocked by the shutdown function of the separator and the lithium ion can not move in the short circuited part. By losing the function, it plays the role of maintaining the safety of the lithium ion secondary battery.
  • the separator may shrink rapidly and the short circuit site of the positive electrode and the negative electrode may be expanded. In this case, the battery temperature may reach a state where it is abnormally overheated to several hundred ° C.
  • the inorganic oxide porous film containing the inorganic oxide filler which has insulation is formed on the surface of the positive electrode which comprises a lithium ion secondary battery, a negative electrode, or a separator.
  • the method for applying the slurry composition for secondary battery separator coating to the separator may be any method capable of uniformly wet coating, and is not particularly limited.
  • capillary coating, spin coating, slit die coating, A spray coating method, a dip coating method, a roll coating method, a screen printing method, a flexographic printing method, a bar coater method, a gravure coater method, a die coater method or the like can be adopted.
  • the method of removing the solvent from the coating is generally a method by drying.
  • the drying temperature of the solvent is preferably a temperature below the softening point of the separator, usually 10 to 200 ° C., preferably 30 to 150 ° C., more preferably 40 to 120 ° C., particularly preferably 50 to 100 ° C., most preferably 60 It is ⁇ 90 ° C.
  • the drying temperature of the solvent is higher than 200 ° C., the function of the separator may be deteriorated, which is not preferable.
  • the resin constituting the composition of the separator is not particularly limited.
  • polyolefin resins such as polyethylene, polypropylene and polybutylene
  • Polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate
  • Polyamide resins such as nylon; polyamide imide resins; polyacetal resins; polystyrene resins; methacrylic resins; polyvinyl chloride resins; polycarbonate resins; polyphenylene sulfide resins, cellulose resins and the like.
  • the shape of the separator is not particularly limited, and examples thereof include a microporous film, a non-woven fabric, and the like.
  • the separator may be surface-coated with a polyvinylidene fluoride resin, a polyaramid resin, or the like before the slurry composition for secondary battery separator coating is applied.
  • the separator may be subjected to a hydrophilization treatment before the slurry composition for secondary battery separator coating is applied. Examples of the hydrophilization treatment include chemical treatment with an acid or an alkali, corona treatment, and plasma treatment.
  • the surface coat film formed by applying and drying the slurry composition for secondary battery separator coat of the present invention on the separator surface may be formed on either side of the separator, or may be formed on both sides.
  • the film thickness of the surface coat film on one side formed by applying and drying the slurry composition for secondary battery separator coat of the present invention on the separator surface for example, usually 0.1 to 30 ⁇ m Preferably, it is 0.3 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, particularly preferably 1 to 4 ⁇ m, and most preferably 1 to 3 ⁇ m. If the film thickness of the surface coat film on one side is less than 0.1 ⁇ m, the heat resistance may be unfavorably deteriorated. If the film thickness of the surface coat film on one side is more than 30 ⁇ m, the function of the separator may be deteriorated, which is not preferable.
  • the thickness of the separator coated with the slurry composition for secondary battery separator coating of the present invention and dried is not particularly limited, but is usually 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m, and more preferably. Is 10 to 30 ⁇ m, particularly preferably 15 to 25 ⁇ m, and most preferably 20 to 25 ⁇ m. If the film thickness of the surface-coated separator is less than 1 ⁇ m, the heat resistance may be unfavorably deteriorated. If the film thickness of the surface coat film on one side is more than 100 ⁇ m, the function of the separator may be deteriorated, which is not preferable.
  • the battery performance is preferable for the battery performance to be excellent when the contact angle of the solvent with respect to the separator coated and dried by coating and drying the slurry composition for secondary battery separator coating of the present invention is in a specific range.
  • the contact angle of water to the separator coated and dried by applying the slurry composition for secondary battery separator coating of the present invention is not particularly limited. For example, after the water is dropped, it usually takes 1600 msec. 60 ° or less, preferably 50 ° or less, more preferably 40 ° or less, further preferably 30 ° or less, particularly preferably 20 ° or less. If the contact angle of water to the surface-coated separator is more than 60 °, battery performance may not be excellent.
  • the contact angle of the electrolytic solution to the separator coated and dried on the surface by applying the slurry composition for secondary battery separator coating of the present invention is no particular limitation on the contact angle of the electrolytic solution to the separator coated and dried on the surface by applying the slurry composition for secondary battery separator coating of the present invention, but for example, when the electrolytic solution is dropped 1600 msec. It is usually at most 80 °, preferably at most 70 °, more preferably at most 60 °, still more preferably at most 55 °, particularly preferably at most 50 °. When the contact angle of the electrolytic solution to the surface-coated separator is more than 80 °, the battery performance may not be excellent.
  • Examples of the electrolytic solution used for measuring the contact angle include alkyl carbonate compounds such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate and the like, and one or more kinds may be used. .
  • the material for a secondary battery of the present invention examples include the positive electrode, the negative electrode, and the separator described above for each use of the above-mentioned secondary battery slurry composition. That is, the positive electrode of the present invention is a positive electrode for a secondary battery having a film for the positive electrode on a current collector, and the film is formed of the non-volatile component of the slurry composition of the secondary battery.
  • the negative electrode of the present invention is a negative electrode for a secondary battery having a film for the negative electrode on a current collector, and the film is formed of the non-volatile component of the slurry composition of the secondary battery.
  • the separator of the present invention is a separator having a film for a separator, and the film is formed of the non-volatile component of the secondary battery slurry composition according to claim 7.
  • the manufacturing method of the material for secondary batteries of the present invention is not particularly limited, for example, a dispersant mixed liquid obtained by mixing the dispersant composition obtained by mixing the components (A) to (D) with a solvent From the step (a) of obtaining the slurry, and the step (b) of mixing the dispersant mixed liquid and the inorganic particles to obtain the slurry composition, the current collector of the positive electrode, the current collector of the negative electrode, the positive electrode, the negative electrode and the separator
  • the production method may include the step (c) of applying the slurry composition to at least one selected and drying it to form a film.
  • step of mixing at least one selected from the component (E) and the other components may be either step (a) or step (b), but when mixed in step (a), the dispersant composition
  • step (a) the dispersant composition
  • the secondary battery of the present invention can be produced using the positive electrode, the negative electrode and the separator produced using the composition for a secondary battery slurry of the present invention, and the production method thereof is not particularly limited.
  • the above-described negative electrode and positive electrode are stacked, wound, folded or stacked according to the battery shape through a separator to produce an electrode body, put in a battery container, and an electrolyte solution injected into the battery container to seal it. May be
  • the shape of the battery is not particularly limited, and examples thereof include coin, cylinder, square, and sheet.
  • the method of packaging the battery is not particularly limited, and examples thereof include a metal case, a mold resin, and an aluminum laminate film.
  • the type of secondary battery is not particularly limited, and is a lithium ion secondary battery such as lithium ion battery, lithium ion polymer battery, all solid lithium ion battery, etc .; alkaline secondary battery such as nickel hydrogen battery, nickel cadmium battery; sodium Sulfur batteries; redox flow batteries; air batteries etc. may be mentioned.
  • the electrolyte solution is not particularly limited, but in the case of a lithium ion battery, for example, one in which a lithium salt is dissolved as a supporting electrolyte in a non-aqueous solvent can be used.
  • the electrolyte in the case where the secondary battery is a nickel hydrogen battery is not particularly limited as long as it is an alkaline aqueous solution, and examples thereof include an aqueous solution containing potassium hydroxide and sodium hydroxide.
  • the secondary battery of the present invention can be used as a power source of various electric devices (including vehicles using electricity).
  • Examples of the electric devices include air conditioners, washing machines, televisions, refrigerators, freezers, cooling devices, laptop computers, tablets, smartphones, computer keyboards, computer displays, desktop computers, CRT monitors, computer racks, printers, integrated computers.
  • Mouse hard disk, computer peripherals, iron, clothes dryer, window fan, walkie-talkie, blower, ventilation fan, music recorder, music player, oven, range, toilet seat with washing function, warm air heater, car component, car navigation system, flashlight, Humidifier, portable karaoke machine, ventilation fan, dryer, dry cell, air purifier, cell phone, emergency light, game machine, sphygmomanometer, coffee mill, coffee maker, kotatsu, copy machine, disc changer, radio, shaver , Juicer, Shredder, Water purifier, Lighting equipment, Dehumidifier, Dishware dryer, Cooker, Stereo, Stove, Speaker, Trouser press, Vacuum cleaner, Body fat scale, Weight scale, Health meter, Movie player, Electric carpet, Electric Kettle, rice cooker, electric
  • Example of this invention is concretely described with the comparative example.
  • the present invention is not limited to these examples.
  • the contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., part number DM-901).
  • thermogravimetry TGA
  • the measurement was performed under the measurement conditions of a setting start temperature of 20 ° C., a setting final temperature of 300 ° C., and a temperature raising rate of 10 ° C./min using a differential thermal balance (manufactured by RIGAKU, part number Thermo plus EVO).
  • Water-insoluble polymer particle component (A) Specific production methods and physical properties of the water-insoluble polymer particle components (A) used in Examples and Comparative Examples are shown in Production Examples A-1 to A-9 in Table 1 below.
  • Water-soluble polymer component (B) The specific production methods and physical properties of the water-soluble polymer components (B) used in Examples and Comparative Examples are shown in Production Examples B-1 to B-5 in Table 2 below.
  • Water-soluble polymer component (C) Specific physical properties of the water-soluble polymer component (C) used in Examples and Comparative Examples are shown in Production Examples C-1 to C-8 in Table 3 below.
  • Polysiloxane type antifoamer 1 Dimethylpolysiloxane, viscosity 100 mPa ⁇ s
  • Polysiloxane type antifoamer 2 Dimethylpolysiloxane, viscosity 1000 mPa ⁇ s
  • Fine silica powder based antifoamer Fine silica powder mineral oil based defoamer hydrophobized with trimethylethoxysilane: Paraffinic mineral oil [Rheology modifier]
  • Inorganic particles Inorganic particles used in Examples and Comparative Examples are shown below.
  • Alpha alumina 1 Primary particle diameter 0.3 ⁇ m
  • BET specific surface area 8.4 m 2 / g ⁇ -alumina 2 Primary particle diameter 0.8 ⁇ m, BET specific surface area 4.9 m 2 / g
  • Gamma alumina Primary particle size 0.3 ⁇ m
  • BET specific surface area 4.7 m 2 / g ⁇ alumina Primary particle size 0.3 ⁇ m
  • Silica Primary particle size 0.3 ⁇ m, BET specific surface area 5.4 m 2 / g Lithium cobaltate; primary particle diameter 7.3 ⁇ m
  • the polymerizable monomer and emulsifier prepared above are mixed and stirred with 150 g of ion-exchanged water with a homogenizer, and reacted at 80 ° C. for 3 hours in a 500 ml separable flask under nitrogen stream to obtain acrylic polymer particles.
  • An emulsion of A-1 was obtained.
  • This acrylic polymer particle A-1 is non-water-soluble and has a nonvolatile content concentration of 40.3% by weight, a viscosity of 30 mPa ⁇ s, an average particle diameter of 166 nm, a zeta potential of ⁇ 45 mV, and a thermogravimetric measurement of 0.3%. Glass transition temperature was -22 ° C.
  • Production Examples A-2 to A-9 polymer particle components are obtained in the same manner as in Production Example A-1, except that the raw materials are changed as shown in Table 1 above in Production Example A-1, respectively. Physical properties and the like were also evaluated in the same manner as in Production Example A-1.
  • Production Example B-1 15 g of acrylic acid, 5 g of acrylonitrile and 80 g of acrylamide were prepared as polymerizable monomers, and 2.0 g of an alkylbenzenesulfonic acid soda salt was prepared as an emulsifier.
  • the polymerizable monomer and emulsifier prepared above are mixed and stirred with 400 g of ion exchanged water with a homogenizer, and reacted at 80 ° C. for 3 hours in a 500 ml separable flask under a nitrogen stream to obtain a water soluble polymer component I got B-1.
  • the water-soluble polymer component B-1 was water-soluble and had a non-volatile content concentration of 20.3% by weight, a viscosity of 18,000 mPa ⁇ s, a thermogravimetric measurement of 5.4%, and a glass transition temperature of 157 ° C.
  • Production Example B-2 to B-5 In Production Example B-2 to B-5, a water-soluble polymer is obtained in the same manner as Production Example B-1 except that the raw materials are changed as shown in Table 2 above in Production Example B-1, respectively. Physical properties and the like were also evaluated in the same manner as in Production Example B-1.
  • Production Example 1 38 g of a polymer particle emulsion containing 15 g of the water-insoluble polymer particle component A-1 which is the component (A), and 25 g of a polymer aqueous solution containing 5 g of the water-soluble polymer component B-1 which is the component (B) 5 g of the water-soluble polymer component C-1 which is the component (C), 15 g of POE (12) lauryl ether, and 307 g of ion-exchanged water are uniformly mixed to obtain a dispersant composition for a secondary battery slurry Obtained.
  • the amount of ion exchange water was 350 g in total with ion exchange water contained in the polymer component.
  • the dispersant composition for secondary battery slurry has a nonvolatile content concentration of 10.3%, a viscosity of 5500 mPa ⁇ s, a pH of 6.7, a surface tension of 33.6 mN / m, a zeta potential of -42 mV, and a foaming power of 80 mm immediately after The value after 5 minutes was 20 mm, the contact angle to the alumina plate as the inorganic oxide plate was 48 ° at 1600 msec, and the contact angle to the polyolefin resin was 21 ° at 1600 msec.
  • Example 1 A secondary battery slurry composition was obtained by uniformly mixing 100 g of ⁇ -alumina 1 which is an inorganic powder, 30 g of a dispersant composition 1 for a secondary battery slurry which is a dispersant, and 100 g of ion exchanged water.
  • the obtained secondary battery slurry composition had a nonvolatile content concentration of 46.6% by weight, a viscosity of 100 mPa ⁇ s, an average particle diameter of 380 nm, a zeta potential of -48 mV, and a foaming power of 15 mm immediately after, 5 minutes after Was 5 mm.
  • Example 11 95 g of lithium cobaltate as an inorganic powder, 5 g of acetylene black, 30 g of a dispersant composition 1 for a secondary battery slurry as a dispersant and 50 g of ion exchanged water are uniformly mixed to obtain a secondary battery slurry composition
  • the obtained secondary battery slurry composition had a nonvolatile content concentration of 68.4% by weight, a viscosity of 6500 mPa ⁇ s, an average particle diameter of 15.4 ⁇ m, a pH of 8.3, a zeta potential of -32 mV, and a foaming power of 15 mm immediately after The value after 5 minutes was 5 mm.
  • the secondary battery slurry composition obtained above was applied to an aluminum foil with a film thickness of 20 ⁇ m and dried in an oven at 150 ° C. to obtain a positive electrode film for a secondary battery.
  • the coated area of the current collector after drying was 95% or more, and the coatability was excellent without cracking on the surface.
  • the drying property was within 300 seconds and was excellent in drying property.
  • the film thickness of the positive electrode coating for a secondary battery was 55 ⁇ m.
  • Example 12 to 19 the secondary battery slurry composition is obtained in the same manner as in Example 11 except that the raw materials are changed as shown in Table 7 in Example 11, and the physical properties and the like are also Example 11 and It evaluated similarly. The results are shown in Table 7.
  • Example 20 A secondary battery slurry composition was obtained by uniformly mixing 95 g of graphite which is an inorganic powder, 5 g of acetylene black, 30 g of the dispersant composition 1 for a secondary battery slurry which is a dispersant, and 50 g of ion exchanged water.
  • the obtained secondary battery slurry composition had a nonvolatile content concentration of 68.2% by weight, a viscosity of 5500 mPa ⁇ s, an average particle diameter of 15.2 ⁇ m, a pH of 7.3, a zeta potential of -40 mV, and a foaming power of 15 mm immediately after The value after 5 minutes was 5 mm.
  • the secondary battery slurry composition obtained above was applied to a copper foil with a film thickness of 18 ⁇ m and dried in an oven at 150 ° C. to obtain a negative electrode film for a secondary battery.
  • the coated area of the current collector after drying was 95% or more, and the coatability was excellent without cracking on the surface.
  • the drying property was within 300 seconds and was excellent in drying property.
  • the film thickness of the negative electrode coating for a secondary battery was 65 ⁇ m.
  • Example 20 to 28 the secondary battery slurry composition is obtained in the same manner as in Example 20 except that the raw materials are changed as shown in Table 8 in Example 20, and the physical properties and the like are also Example 20 and It evaluated similarly. The results are shown in Table 8.
  • Example 29 2 g of a polymer aqueous solution containing 0.4 g of a water-soluble polymer component B-1 which is a component (B), 0.4 g of a water-soluble polymer component C-1 which is a component (C), POE (12) 15 g of lauryl ether and 97 g of ion-exchanged water were mixed, and 3 g of a polymer particle emulsion containing 1.2 g of the water-insoluble polymer particle component A-1 which is the component (A) was further added and uniformly mixed. Next, 100 g of the inorganic powder ⁇ -alumina 1 was further added and uniformly mixed to obtain a secondary battery slurry composition.
  • the obtained dispersant composition for a secondary battery slurry had a non-volatile content concentration of 10.3%, a viscosity of 5500 mPa ⁇ s, a pH of 6.7, a surface tension of 33.6 mN / m, a zeta potential of -42 mV, and a foaming power immediately after
  • the value was 80 mm, the value after 5 minutes was 20 mm, the contact angle to the alumina plate as the inorganic oxide plate was 48 ° at 1600 msec, and the contact angle to the polyolefin resin was 21 ° at 1600 msec.
  • the secondary battery slurry composition obtained above was applied to a polyolefin resin separator with a film thickness of 20 ⁇ m, and dried in an oven at 80 ° C.
  • the surface area of the separator surface coated after drying was 95% or more, and the coatability was excellent.
  • the surface coat film thickness was 5 ⁇ m.
  • the surface-coated separator obtained by surface-coating the separator surface has a shrinkage ratio of 95% or more, and is excellent in heat resistance.
  • Example 30 2 g of a polymer aqueous solution containing 0.4 g of a water-soluble polymer component B-1 which is a component (B), 0.4 g of a water-soluble polymer component C-1 which is a component (C), POE (12) 15 g of lauryl ether and 97 g of ion-exchanged water were mixed, and 3 g of a polymer particle emulsion containing 1.2 g of the water-insoluble polymer particle component A-1 which is the component (A) was further added and uniformly mixed. Next, 95 g of graphite which is an inorganic powder and 5 g of acetylene black were further added and uniformly mixed to obtain a secondary battery slurry composition.
  • the obtained secondary battery slurry composition had a nonvolatile content concentration of 68.4% by weight, a viscosity of 6500 mPa ⁇ s, an average particle size of 15.4 ⁇ m, a pH of 8.4, a zeta potential of -45 mV, and a foaming power of 15 mm immediately after The value after 5 minutes was 5 mm.
  • the dispersion stability of the dispersant composition for secondary battery slurries was evaluated using this secondary battery slurry composition, the weight of the sediment was less than 5% by weight, and the dispersion stability was excellent.
  • the secondary battery slurry composition obtained above was applied to a copper foil with a film thickness of 18 ⁇ m and dried in an oven at 150 ° C.
  • the coated area of the current collector after drying was 95% or more, and the coatability was excellent without cracking on the surface.
  • the drying property was within 300 seconds and was excellent in drying property.
  • the film thickness of the negative electrode coating for a secondary battery was 70 ⁇ m.
  • An equivalent mixed solution of ethylene carbonate and dimethyl carbonate was dropped onto the surface of the negative electrode film for a secondary battery, and the contact angle was measured after 1600 msec. The contact angle was less than 20 °, and the retention of the electrolyte was excellent.
  • a secondary battery slurry composition was obtained by uniformly mixing 100 g of ⁇ -alumina 1 which is an inorganic powder, 30 g of a dispersant composition 9 for a secondary battery slurry which is a dispersant, and 100 g of ion exchanged water.
  • the obtained secondary battery slurry composition had a nonvolatile content concentration of 46.4% by weight, a viscosity of 60 mPa ⁇ s, an average particle diameter of 660 nm, a zeta potential of -10 mV, and a foaming power of 10 mm immediately after, 5 minutes after Was 5 mm.
  • the weight of the sediment is 10% by weight or more and less than 30% by weight, and the dispersion stability is poor.
  • the secondary battery slurry composition obtained above was applied to a polyolefin resin separator with a film thickness of 20 ⁇ m, and dried in an oven at 80 ° C. The coated area of the surface of the separator after drying is less than 80%, and the coatability is poor. The surface coat film thickness was 2 ⁇ m. The film for secondary batteries which surface-coated the separator surface is less than 80% of a contraction rate, and is inferior to heat resistance.
  • Comparative Examples 2 to 8 a secondary battery slurry composition is obtained in the same manner as in Comparative Example 1 except that the raw materials are changed as shown in Tables 9 and 10 in Comparative Example 1, and the physical properties and the like are also compared. It evaluated similarly to Example 1. The results are shown in Tables 9 and 10.
  • the slurry compositions for secondary batteries of Examples 1 to 27 are dispersant compositions containing the above component (B), the above component (C) and the above component (D).
  • the content of the component (D) is 0.1 to 500 parts by weight
  • the glass transition temperature of the component (B) is Tg (B) (° C.)
  • the glass transition temperature of the component (C) is Tg (C) (2) Since it is referred to as (degree C) and is a dispersant composition for secondary battery slurries which satisfies following Numerical formula (I), it is excellent in coating property and the drying property of a film.
  • the secondary battery slurry composition was applied to the surface of the current collector at 10 mg / cm 2 and dried by heating to a temperature of 150 ° C.
  • the coated area of the current collector surface was measured.
  • the evaluation criteria for coatability are as follows. :: The coated area is 95% or more and the coating property is excellent without cracking of the coated surface upon drying. X: Cracking of the applied surface occurs upon drying, and the coated area is less than 95%, resulting in poor coatability.
  • the secondary battery slurry composition is applied to the current collector surface at 10 mg / cm 2, and the time until the coated surface dries at a temperature of 150 ° C. is visually measured. Evaluation criteria of dryness are as follows. ⁇ : If the drying time is 300 seconds or less, the waiting time is small and the drying property is good. X: If the drying time is more than 300 seconds, the waiting time is long and the workability is impaired, so the drying property is not good.

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Abstract

L'invention fournit une composition d'agent de dispersion pour bouillie de batterie secondaire de stabilité de dispersion satisfaisante, une composition de bouillie de batterie secondaire dotée de propriétés satisfaisantes en termes d'application et de séchage de film de revêtement, un procédé de fabrication de composition de bouillie de batterie secondaire dotée de propriétés satisfaisantes en termes d'application et de séchage de film de revêtement, et une batterie mettant en œuvre cette composition de bouillie de batterie secondaire. La composition d'agent de dispersion pour bouillie de batterie secondaire de l'invention comprend les composants (B) à (D) définis ci-après, la proportion massique de composant (C) par rapport audit composant (B) étant comprise entre ０,５ et ３,５, et la teneur en composant tensioactif (D) étant comprise entre 0,1 et 500 parties en masse lorsque la teneur totale en composant (B) et en composant (C) équivaut à 100 parties en masse. Composant (B) : composant polymère hydrosoluble contenant 70% en masse ou plus d'une unité monomère à teneur en azote ; et composant (C) : composant polymère hydrosoluble de degré de polymérisation compris entre 100 et 10000, et contenant 60 à 99% d'au moins un élément choisi parmi un monomère (I) comprenant un groupe carboxyle et une unité monomère (IV) comprenant un groupe hydroxy.
PCT/JP2018/036267 2017-10-10 2018-09-28 Composition d'agent de dispersion pour bouillie de batterie secondaire, et application de celle-ci Ceased WO2019073820A1 (fr)

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JP2022528479A (ja) * 2019-09-23 2022-06-10 エルジー エナジー ソリューション リミテッド リチウム二次電池負極用のバインダー及びそれを含むリチウム二次電池用の負極
JP2022530458A (ja) * 2019-04-26 2022-06-29 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 多孔質集電体上に堆積されたコンフォーマルコーティングを有する電極
WO2023085233A1 (fr) * 2021-11-09 2023-05-19 株式会社日本触媒 Composition d'électrode négative de batterie secondaire au lithium-ion
CN116918160A (zh) * 2022-06-24 2023-10-20 宁德时代新能源科技股份有限公司 隔离膜、其制备方法及其相关的二次电池和用电装置
WO2025033219A1 (fr) * 2023-08-09 2025-02-13 東亞合成株式会社 Liant pour électrode de batterie secondaire et utilisation associée
JP2025524512A (ja) * 2022-12-26 2025-07-30 エルジー エナジー ソリューション リミテッド リチウム二次電池用電極組成物、電極スラリー、電極、およびリチウム二次電池

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