WO2012133030A1 - Composition aqueuse pour former une électrode d'accumulateur, électrode d'accumulateur et accumulateur associés - Google Patents

Composition aqueuse pour former une électrode d'accumulateur, électrode d'accumulateur et accumulateur associés Download PDF

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Publication number
WO2012133030A1
WO2012133030A1 PCT/JP2012/057143 JP2012057143W WO2012133030A1 WO 2012133030 A1 WO2012133030 A1 WO 2012133030A1 JP 2012057143 W JP2012057143 W JP 2012057143W WO 2012133030 A1 WO2012133030 A1 WO 2012133030A1
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Prior art keywords
ethylenically unsaturated
group
electrode
weight
secondary battery
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PCT/JP2012/057143
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English (en)
Japanese (ja)
Inventor
大 稲垣
浩一郎 宮嶋
順幸 諸石
真吾 池田
一成 春田
幸子 成廣
隆明 小池
安紀子 仁科
隆明 大竹
Original Assignee
東洋インキＳｃホールディングス株式会社
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Priority to JP2012545962A priority Critical patent/JP5252134B2/ja
Publication of WO2012133030A1 publication Critical patent/WO2012133030A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an aqueous composition for forming a secondary battery electrode, an electrode obtained using the composition, and a secondary battery obtained using the electrode.
  • An important characteristic required for the composite ink used for forming the electrode and the composition for forming the underlayer includes uniformity when the active material and the conductive additive are dispersed. This is because the dispersion state of the active material and the conductive auxiliary in the composition ink and the underlayer forming composition is the distribution state of the active material and the conductive auxiliary in the composite layer and the distribution state of the conductive auxiliary in the underlayer. This is because it affects the physical properties of the electrode and the battery performance.
  • the dispersion of the active material and the conductive aid is an important issue.
  • carbon materials (conducting aids) with excellent conductivity have a strong cohesive force due to their large structure and specific surface area, and evenly mix and disperse, whether in mixed ink or in the composition for forming the underlayer. Is difficult.
  • the dispersibility and particle size control of the carbon material that is the conductive auxiliary agent is insufficient, the internal resistance of the electrode cannot be reduced because a uniform conductive network is not formed, and as a result, the performance of the electrode material is sufficient. The problem of being unable to withdraw.
  • the active material is not sufficiently dispersed in the composite ink as well as the conductive auxiliary agent, partial aggregation occurs in the composite layer formed from such a composite ink.
  • This partial aggregation causes a resistance distribution on the electrode, and as a result, current concentration occurs when used as a battery, which may cause problems such as partial heat generation and deterioration.
  • the composite ink and the underlayer forming composition are required to have appropriate fluidity so as to be coated on the surface of the metal foil functioning as a current collector. Furthermore, in order to form a composite material layer or a base layer having a surface that is as flat as possible and having a uniform thickness, the composite ink or the base layer forming composition is required to have an appropriate viscosity.
  • the base layer After the formation of the composite layer formed from the composite ink and the composition for forming the base layer, the base layer is cut into pieces of a desired size and shape together with the metal foil as the base material, It is punched out. Therefore, the material layer and the base layer are required to have hardness that does not damage and softness that does not crack or peel off by cutting or punching.
  • the composite material layer and the underlayer are exposed to the electrolyte in the battery, the composite material layer and the underlayer may be collapsed and peeled off from the current collector. Therefore, elution resistance in the electrolytic solution is also required for the composite material layer and the underlayer.
  • Patent Documents 1 to 4 an active material and a conductive material are mixed, and this mixture is kneaded with a cellulose-based thickener aqueous solution, and then an aqueous binder such as tetrafluoropolyethylene or latex is further added and further kneaded. It is disclosed that a composite ink is obtained. However, these composite inks have a problem that the dispersed state is insufficient and the flexibility is poor, and a desired electrode cannot be produced, so that good battery performance cannot be obtained.
  • the object of the present invention is to improve the dispersibility and rheological properties of the active material and conductive additive in the electrode-forming composition, and to adhere the layer formed from the electrode-forming composition to the current collector. It is to improve the strength of the coating film, the flexibility of the coating film, and the elution resistance of the electrolytic solution, and further to improve the battery cycle test performance.
  • This invention solves the said subject by using the anionic dispersing agent (A) excellent in the dispersibility of an electrode active material and a conductive support agent.
  • An aqueous composition for forming a secondary battery electrode comprising at least one of a carbon material that is an electrode active material or a conductive additive, an anionic dispersant (A), and water,
  • the anionic dispersant (A) has at least one of carboxylic acid or sulfonic acid as an anionic site, an acid value of 100 to 600 mgKOH / g, a hydroxyl value of 0 to 400 mgKOH / g, and a weight average molecular weight.
  • the aqueous composition for secondary battery electrode formation whose is 5,000 or more.
  • composition according to [5] above, wherein the cross-linked resin fine particles are resin fine particles obtained by emulsion polymerization of the following monomers in water in the presence of a surfactant with a radical polymerization initiator.
  • C1 From the group consisting of an ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group and a monomer (c2) having two or more ethylenically unsaturated groups in one molecule At least one monomer selected: 0.1 to 5% by weight (C2) Ethylenically unsaturated monomer (c3) other than the monomers (c1) to (c2): 95 to 99.9% by weight (However, the total of the above (c1) to (c3) is 100% by weight.)
  • composition according to [6] above, wherein the ethylenically unsaturated monomer (c3) has the following composition.
  • Ethylenically unsaturated monomer (c4) having a monofunctional or polyfunctional epoxy group
  • ethylenically unsaturated monomer (c5) having a monofunctional or polyfunctional amide group
  • ethylene having a monofunctional or polyfunctional hydroxyl group
  • composition according to [7] above, wherein the ethylenically unsaturated monomer (c7) has the following composition. At least one monomer selected from the group consisting of an ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms and an ethylenically unsaturated monomer (c9) having a cyclic structure: 30 ⁇ 95% by weight Ethylenically unsaturated monomers other than (c1) to (c6), (c8) and (c9): 0 to 69.8% by weight (However, the total of the above (c1) to (c3) is 100% by weight.)
  • the binder composition (C) is at least one selected from the group consisting of an uncrosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound.
  • An electrode for a secondary battery comprising a current collector and at least one of a composite material layer or an electrode underlayer formed from the composition described in [1] to [10] above.
  • a secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the secondary battery electrode according to [11].
  • a lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution, wherein at least one of the positive electrode and the negative electrode is the secondary battery electrode according to [11].
  • an electrode-forming composition having excellent rheological properties and dispersed state can be obtained. Furthermore, by preparing a composite material layer and an underlayer with this electrode forming composition, the adhesion to the current collector, the strength of the coating film, the flexibility of the coating film, and the resistance to electrolytic solution elution are improved. Cycle test performance can be improved.
  • the electrode for the secondary battery can be obtained by various methods. For example, on the surface of a current collector such as a metal foil, (1) an ink-like composition containing an active material and a liquid medium (hereinafter referred to as a composite ink), or (2) an active material, a conductive auxiliary agent, and a liquid A composite ink containing a medium, (3) a composite ink containing an active material, a binder and a liquid medium, and (4) a composite ink containing an active material, a conductive additive, a binder and a liquid medium.
  • a composite ink an ink-like composition containing an active material and a liquid medium
  • an electrode underlayer is formed on the surface of the current collector of the metal foil using a composition for forming an underlayer containing a conductive additive and a liquid medium, and the above composite ink (1 ) To (4) and other composite inks can be used to form a composite layer to obtain an electrode.
  • the dispersion state of the active material and the conductive aid and the electrolytic solution elution resistance of the electrode mixture layer and the base layer influence the battery performance.
  • the anionic dispersant (A) relaxes the aggregation of the active material or functions as a dispersant for the carbon material that is a conductive additive. Therefore, the aqueous composition for forming a secondary battery electrode of the present invention can be used as a composite ink that requires an active material or a composition for forming an underlayer that does not require an active material.
  • the anionic dispersant (A) in the present invention has at least one of carboxylic acid or sulfonic acid as an anionic site, an acid value of 100 to 600 mgKOH / g, and a hydroxyl value of 0 to 400 mgKOH / g. It is a resin-type dispersant having a weight average molecular weight of 5000 or more.
  • the anionic dispersant (A) having sulfonic acid is not particularly limited as long as it is a resin having sulfonic acid.
  • a formalin condensate of aromatic sulfonic acid can be used.
  • a formalin condensate of aromatic sulfonic acid is, for example, a product obtained by condensing benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid (or an alkali metal salt thereof) with formalin.
  • the ethylenically unsaturated monomer (a1) which has an aromatic ring the ethylenically unsaturated monomer (a2) which has a carboxyl group, (a1) And a resin-type dispersant obtained by copolymerization with an ethylenically unsaturated monomer (a3) other than (a2).
  • the monomer (a1) is an optional component.
  • the ethylenically unsaturated monomer constituting the anionic dispersant (A) in the present invention indicates a monomer having one ethylenically unsaturated group in one molecule.
  • the ethylenically unsaturated monomer (a1) having an aromatic ring is not particularly limited as long as it is a monomer having an aromatic ring, and examples thereof include styrene, ⁇ -methylstyrene, and benzyl (meth) acrylate. .
  • the ethylenically unsaturated monomer (a2) having a carboxyl group is not particularly limited as long as it is a monomer having a carboxyl group, but maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl thereof.
  • Monoester ⁇ - (meth) acryloxyethyl monoester phthalate, ⁇ - (meth) acryloxyethyl monoester isophthalate, ⁇ - (meth) acryloxyethyl monoester terephthalate, ⁇ - (meth) acrylate succinate
  • Examples include loxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like. In particular, methacrylic acid and acrylic acid are preferable.
  • (meth) acrylate compounds include alkyl (meth) acrylates and alkylene glycol (meth) acrylates.
  • alkyl-based (meth) acrylate examples include alkyl (meth) acrylate having 1 to 22 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like.
  • alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate is exemplified.
  • alkylene glycol-based (meth) acrylate examples include a monoacrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain, such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, or a corresponding monoacrylate.
  • methacrylate methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the end and having a polyoxyalkylene chain, or the corresponding monomethacrylate, phenoxyethylene glycol
  • methacrylate methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, monoacrylate having an alkoxy group at the end and having a polyoxyalkylene chain, or the corresponding monomethacrylate, phenoxyethylene glycol
  • polyoxyalkylene-based acrylates having a phenoxy or aryloxy group at the terminal such as (meth) acrylates, or corresponding methacrylates.
  • hydroxyl-containing unsaturated compounds other than the above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene Etc.
  • Nitrogen-containing unsaturated compounds other than those mentioned above include, for example, acrylamide unsaturated compounds, and monoalkylols such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide (meta) ) Acrylamide, dialalkylol (meth) acrylamide such as N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide and the like.
  • monoalkylols such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide (meta) ) Acrylamide, dialalkylol (meth) acrylamide such as N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acryl
  • unsaturated compounds include, for example, perfluoroalkyl group-containing vinyl monomers such as perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2- Perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms such as perfluorohexylethyl (meth) acrylate; perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluoro Perfluoroalkylalkylenes such as decylethylene and the like, and as vinyl compounds containing silanol groups, vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltol Ethoxysilane, .gamma. (meth) acryloxy propyl trimeth
  • fatty acid vinyl compound examples include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.
  • alkyl vinyl ether compound examples include butyl vinyl ether and ethyl vinyl ether.
  • Examples of the ⁇ -olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.
  • vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, ⁇ -methylstyrene, 2-methylstyrene, chlorostyrene, and the like. It is done.
  • ethynyl compound examples include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.
  • the ratio of the ethylenically unsaturated monomer constituting the copolymer in the anionic dispersant (A) used in the present invention is the case where the total of the monomers (a1) to (a3) is 100% by weight.
  • the other monomer (a3) other than (a1) to (a2) is preferably 0 to 70% by weight.
  • an ethylenically unsaturated monomer (a1) having an aromatic ring 40 to 75% by weight of the ethylenically unsaturated monomer (a2) having a carboxyl group
  • the other monomer (a3) other than the above (a1) to (a2) is 0 to 50% by weight.
  • the anionic dispersant (A) is produced by polymerizing or condensing a monomer having a carboxyl group or a sulfonic acid group, but is a single monomer having an anionic functional group in the whole molecule of the anionic dispersant (A).
  • the composition ratio of the body is represented by an acid value, the following is preferable. That is, the acid value of the anionic dispersant (A) used is preferably in the range of 100 mgKOH / g to 600 mgKOH / g, and more preferably in the range of 300 mgKOH / g to 600 mgKOH / g.
  • the acid value of the anionic dispersant (A) is lower than the above range, the dispersion stability of the dispersion tends to decrease and the viscosity tends to increase. Moreover, when an acid value is higher than the above-mentioned range, the adhesive force of the anionic dispersing agent (A) with respect to the pigment surface will fall, and there exists a tendency for the storage stability of a dispersion to fall.
  • the acid value is a value obtained by converting the acid value (mgKOH / g) measured in accordance with the potentiometric titration method of JIS K 0070 into a solid content.
  • the hydroxyl value of the anionic dispersant (A) is preferably 0 mgKOH / g or more and 400 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 250 mgKOH / g or less.
  • the hydroxyl value is 400 mgKOH / g or more, the interaction between molecules in the aqueous medium becomes stronger, and the viscosity of the dispersant solution becomes higher than necessary, so that the dispersibility of the conductive carbon or the active material is deteriorated. There is.
  • the weight average molecular weight of the anionic dispersant (A) is preferably 5000 or more. More preferably, it is 30000 or more. Moreover, the upper limit is preferably 1500,000 or less, and more preferably 800,000 or less. When the weight average molecular weight is less than 5,000, there is a possibility of causing poor dispersion of the carbon material that is the electrode active material or the conductive auxiliary agent, and when it is less than 30,000, there is a possibility that deterioration of the electrolyte dissolution property may be caused.
  • the anionic dispersant (A) can be obtained by various production methods.
  • the monomers (a1) to (a3) are polymerized in an organic solvent that can be azeotroped with water. Thereafter, an aqueous liquid medium typified by water and a neutralizing agent are added to neutralize at least a part of the sulfonic acid group or carboxyl group, the azeotropic solvent is distilled off, and the anionic dispersant (A ) Aqueous solution or dispersion.
  • the organic solvent for the polymerization may be any one that azeotropes with water, but is preferably highly soluble in the resulting dispersant resin, preferably ethanol, 1-propanol, 2-propanol, 1-butanol. 1-butanol is more preferable.
  • the above monomers are polymerized in a hydrophilic organic solvent, and then neutralized and aqueousized by adding water and a neutralizing agent (the hydrophilic organic solvent is not distilled off).
  • a liquid in which the anionic dispersant (A) is dissolved or dispersed in an aqueous liquid medium containing can be obtained.
  • the hydrophilic organic solvent used is preferably one having high solubility in the resulting dispersant resin, preferably glycol ethers, diols, more preferably (poly) alkylene glycol monoalkyl ether, carbon number. 3-6 alkanediols are preferred.
  • Examples of the neutralizing agent used for neutralization in the above production process include various organic amines such as aqueous ammonia, dimethylaminoethanol, diethanolamine, and triethanolamine, and alkalis such as sodium hydroxide, lithium hydroxide, and potassium hydroxide.
  • organic amines such as aqueous ammonia, dimethylaminoethanol, diethanolamine, and triethanolamine
  • alkalis such as sodium hydroxide, lithium hydroxide, and potassium hydroxide.
  • An inorganic alkali agent such as a metal hydroxide can be used.
  • a neutralizing agent can also be added to the anionic dispersant.
  • the salt of the acidic functional group is easily dissociated in an aqueous medium, and is more easily charged. Therefore, the surface of the conductive carbon and the surface of the positive and negative electrode active materials on which the neutralized anionic dispersant is adsorbed are charged, and dispersibility is further improved by the repulsion.
  • Examples of the base used for this neutralization include inorganic bases such as ammonia, LiOH, NaOH, and KOH, and propylamine, isoamylamine, hexylamine, 2-ethylhexylamine, 3-ethoxypropylamine, 2-ethylhexyl.
  • Organic bases such as siloxypropylamine, 3-lauryloxypropylamine, 3-aminopropanol, dimethylamine, diisopropylamine, 2-piperidineethanol, trimethylamine, ethanolamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, and triethylamine ( Amine compounds). Dimethylethanolamine, ammonia, and NaOH are preferable, and ammonia or NaOH is more preferable.
  • the amount of the base used for the anionic dispersant having an acidic functional group is preferably 0.1 to 10 equivalents, more preferably 0.8 to 1 of the acidic functional group of the anionic dispersant used. .2 equivalents.
  • the dispersant resin acts (for example, adsorbs) on the active material or the carbon material via the aromatic ring, and is neutralized, whereby the active material or the carbon material is repelled by the charge repulsion of the ionized carboxyl group or sulfonic acid group. It is considered that the dispersion state of the material in the aqueous liquid medium can be kept stable.
  • ⁇ Cellulose-based thickener (B)> Although it does not specifically limit as a cellulose thickener (B), For example, carboxymethylcellulose (CMC), carboxyethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), ethylhydroxyethylcellulose (EHEC), hydroxymethyl, for example. Examples include ethyl cellulose, hydroxyhydroxypropyl methyl cellulose, methyl cellulose (MC), and hydroxyalkyl methyl cellulose.
  • CMC carboxymethylcellulose
  • HEC hydroxyethylcellulose
  • HPC hydroxypropylcellulose
  • EHEC ethylhydroxyethylcellulose
  • hydroxymethyl for example.
  • examples include ethyl cellulose, hydroxyhydroxypropyl methyl cellulose, methyl cellulose (MC), and hydroxyalkyl methyl cellulose.
  • Cellulose in pulp is a polysaccharide to which anhydroglucose monomer units are bonded, and has three hydroxy groups in one glucose monomer unit.
  • the substituent that is substituted with one or more of the hydroxy groups can be selected without any particular limitation, but is a hydrophilic substituent in order to be a water-soluble cellulose-based thickener (B). It is preferable.
  • a carboxyalkyl group and a hydroxyalkyl group are preferable, and a hydroxyalkyl group is particularly preferable.
  • the number of substituents substituted with hydroxy groups in cellulose is not particularly limited, but it is preferable that 0.5 or more of three hydroxy groups of one glucose monomer unit are substituted.
  • the average degree of polymerization of the cellulosic thickener (B) can be selected without any particular limitation.
  • the added dispersant (A) acts (for example, adsorbs) on the surface of the carbon material and the surface of the active material, so that the carbon material surface and the surface of the active material material are wetted with the solvent. It is considered that the dispersion state and rheological properties are improved by solving the aggregation of the carbon material and the active material.
  • the dispersant (A) when used in combination with the cellulose-based thickener (B), the dispersibility and rheological properties by the dispersant (A) and the thickening effect by the cellulose-based thickener (B) are impaired. It can function without being disintegrated and exhibit even higher dispersion stability. At this time, the dispersant (A) is more likely to act (for example, adsorb) on the surface of the carbon material and the active material, so that it exhibits a dispersibility improving effect and a rheological property improving effect, and the cellulose-based thickener (B) Is considered to exert a thickening effect mainly.
  • Cellulosic thickener (B) can be used in combination with dispersant (A) regardless of whether it is anionic or nonionic, but considering the dispersibility improvement effect and rheological property improvement effect of compound ink In this case, the nonionic cellulose thickener (B) is more preferable. This is because the nonionic cellulose-based thickener (B) has a lower effect on the surface of the carbon material and the active material surface, and thus the dispersion effect, so that when used in combination with the dispersant (A), the function is further separated. It seems to work.
  • the dispersant (A) having a charge has high hydrophilicity and is compatible with the cellulosic thickener (B). Therefore, it is possible to form a composite ink coating film without phase separation of the dispersant (A) and the cellulose-based thickener (B) during the drying process of the composite ink. It is considered that the mixing of is more uniform and the coating becomes stronger. As a result, the strength of the composite material layer is increased, and it is considered that cracking when the composite material layer is thickened is improved (flexibility is improved).
  • the binder composition (C) it is preferable to include cross-linked resin fine particles.
  • the crosslinked resin fine particles are resin fine particles having an internal cross-linked structure (three-dimensional cross-linked structure), and it is important that the fine particles are cross-linked inside the particles.
  • the cross-linked resin fine particles have a cross-linked structure, the electrolytic solution elution resistance can be improved, and the effect can be enhanced by adjusting the cross-linking inside the particles.
  • the cross-linked resin fine particles contain a specific functional group, it is possible to contribute to adhesion with the current collector or the electrode.
  • the composition for secondary battery electrode formation excellent in flexibility can be obtained by adjusting the quantity of a crosslinked structure and a functional group. Furthermore, the flexibility of the binder can also be adjusted by adding a crosslinking agent and utilizing crosslinking between particles (crosslinking between particles). In this case, since the leakage of the cross-linking agent component to the electrolytic solution and variations in electrode production may occur, it is necessary to use the cross-linking agent to such an extent that the resistance to the electrolytic solution is not impaired.
  • crosslinked resin fine particles used in the electrode-forming composition of the present invention include resin fine particles obtained by emulsion polymerization of an ethylenically unsaturated monomer in water in the presence of a surfactant with a radical polymerization initiator. Is mentioned.
  • Such crosslinked resin fine particles are preferably obtained by emulsion polymerization of an ethylenically unsaturated monomer containing the following monomers (C1) and (C2) in the following proportions.
  • (C1) From the group consisting of an ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group and a monomer (c2) having two or more ethylenically unsaturated groups in one molecule At least one monomer selected: 0.1 to 5% by weight (C2) Ethylenically unsaturated monomer (c3) other than the monomers (c1) to (c2): 95 to 99.9% by weight (However, the total of the above (c1) to (c3) is 100% by weight.)
  • (c1) and (c3) indicate monomers having one ethylenically unsaturated group in one molecule unless otherwise specified. .
  • the functional group (alkoxysilyl group, ethylenically unsaturated group) possessed by the monomer contained in the monomer group (C1) is a self-crosslinking reactive functional group, and is mainly used for particle internal crosslinking during particle synthesis. Has the effect of forming. Electrolytic solution resistance can be improved by sufficiently carrying out internal crosslinking of the particles. Therefore, it is possible to obtain crosslinked resin fine particles by using a monomer contained in the monomer group (C1). In addition, by sufficiently carrying out particle crosslinking, the resistance to electrolytic solution can be improved.
  • Examples of the ethylenically unsaturated monomer (c1) having a monofunctional or polyfunctional alkoxysilyl group include ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, and ⁇ -methacryloxypropyltributoxy.
  • Silane ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, ⁇ - Examples include methacryloxymethyltrimethoxysilane, ⁇ -acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinylmethyldimethoxysilane. That.
  • Examples of the monomer (c2) having two or more ethylenically unsaturated groups in one molecule include allyl (meth) acrylate, 1-methylallyl (meth) acrylate, and 2-methylallyl (meth) acrylate.
  • the purpose of the alkoxysilyl group or ethylenically unsaturated group in the monomer (c1) or monomer (c2) is to introduce a cross-linked structure into the particle by self-condensation or polymerization mainly during the polymerization. However, a part of it may remain inside or on the surface after polymerization. The remaining alkoxysilyl group or ethylenically unsaturated group contributes to interparticle crosslinking of the binder composition. In particular, an alkoxysilyl group is preferable because it has an effect of improving adhesion to the current collector.
  • the monomer classified into the monomer group (C1) is used in an amount of 0.1 to 5% by weight in the whole ethylenically unsaturated monomer (100% by weight in total) used for emulsion polymerization. And preferably 0.5 to 3% by weight.
  • the monomer classified into the monomer group (C1) is less than 0.1% by weight, the particles are not sufficiently crosslinked, and the resistance to the electrolytic solution is deteriorated.
  • it exceeds 5% by weight there will be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there will be a problem in the storage stability.
  • the crosslinked resin fine particles used in the binder composition include a monomer group (C2) other than the monomers (c1) and (c2).
  • the monomer (c3) having an ethylenically unsaturated group can be obtained by emulsion polymerization at the same time.
  • the monomer (c3) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group other than the monomers (c1) and (c2).
  • At least one monomer selected from the group consisting of (c6), and a monomer having an ethylenically unsaturated group other than the monomers (c1), (c2), (c4) to (c6) ( c7) can be used.
  • an epoxy group, an amide group, or a hydroxyl group can be left in or on the surface of the cross-linked resin fine particles, and thereby adherence to the current collector.
  • the physical properties such as can be improved.
  • the functional groups of the monomers (c4) to (c6) are likely to remain inside or on the surface even after the particle synthesis, and the adhesion effect to the current collector is large even in a small amount.
  • a part of them may be used for the crosslinking reaction, and by adjusting the degree of crosslinking of these functional groups, it is possible to balance the resistance to electrolytic solution and the adhesion.
  • Examples of the ethylenically unsaturated monomer (c4) having a monofunctional or polyfunctional epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate.
  • Examples of the monomer ethylenically unsaturated (c5) having a monofunctional or polyfunctional amide group include, for example, a primary amide group-containing ethylenically unsaturated monomer such as (meth) acrylamide; N-methylolacrylamide, N, Alkylol (meth) acrylamides such as N-di (methylol) acrylamide and N-methylol-N-methoxymethyl (meth) acrylamide; N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, Monoalkoxy (meth) acrylamides such as N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide; N, N-di (methoxymethyl) acrylamide N-ethoxymethyl-N-methoxy Tylmethacrylamide, N, N-di (ethoxymethyl
  • Examples of the ethylenically unsaturated monomer (c6) having a monofunctional or polyfunctional hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol.
  • a part of the functional groups of the monomers classified into monomers (c4) to (c6) may react during particle polymerization and be used for intraparticle crosslinking.
  • the monomers classified into the monomers (c4) to (c6) are 0.1 to 20% by weight in the whole ethylenically unsaturated monomers (100% by weight in total) used for emulsion polymerization. %, Preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight.
  • the amount of the monomers (c4) to (c6) is less than 0.1% by weight, the amount of functional groups remaining in the interior of the particles or on the surface after polymerization is reduced, and the adhesion to the current collector is improved. Cannot contribute enough.
  • it exceeds 20% by weight there will be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there will be a problem in the storage stability.
  • the monomer (c7) is not particularly limited as long as it is a monomer other than the monomers (c1), (c2), (c4) to (c6) and has an ethylenically unsaturated group, Examples thereof include an ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms and an ethylenically unsaturated monomer (c9) having a cyclic structure.
  • the monomers (c8) and (c9) are all monomers having an ethylenically unsaturated group ((c1), (c2), (c4) to (c6) and (c7)).
  • a total of 30 to 95% by weight is preferably contained therein. It is preferable to use the monomer (c8) or the monomer (c9) because the particle stability during particle synthesis and the resistance to electrolytic solution are excellent. If it is less than 30% by weight, the electrolyte solution resistance may be adversely affected. If it exceeds 95% by weight, the stability during particle synthesis will be adversely affected, or even if synthesis is possible, the temporal stability of the particles will be impaired. There is a case.
  • Examples of the ethylenically unsaturated monomer (c8) having an alkyl group having 8 to 18 carbon atoms include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, and cetyl (meth) acrylate. And stearyl (meth) acrylate.
  • Examples of the ethylenically unsaturated monomer (c9) having a cyclic structure include alicyclic ethylenically unsaturated monomers and aromatic ethylenically unsaturated monomers.
  • Examples of the alicyclic ethylenically unsaturated monomer include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, and examples of the aromatic ethylenically unsaturated monomer include benzyl (meth) acrylate.
  • Phenoxyethyl (meth) acrylate styrene, ⁇ -methylstyrene, 2-methylstyrene, chlorostyrene, allylbenzene, ethynylbenzene and the like.
  • Examples of monomers other than the monomer (c8) and monomer (c9) classified as monomer (c7) include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meta).
  • Examples of monomers other than the monomer (c8) and monomer (c9) classified as monomer (c7) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or , These alkyl or alkenyl monoesters, phthalic acid ⁇ - (meth) acryloxyethyl monoester, isophthalic acid ⁇ - (meth) acryloxyethyl monoester, terephthalic acid ⁇ - (meth) acryloxyethyl monoester, succinic acid Carboxyl group-containing ethylenically unsaturated monomers such as ⁇ - (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid; tertiary butyl groups such as tertiary butyl (meth) acrylate Ethylenically unsaturated monomer: Ethylene sulfonic acid group-containing ethylene such as vinyl
  • a polyfunctional hydrazide compound having two or more hydrazide groups capable of reacting with a keto group as a crosslinking agent is mixed with the binder composition.
  • a tough coating film can be obtained by crosslinking between a keto group and a hydrazide group.
  • This coating film has excellent electrolytic solution resistance and binding properties. Furthermore, since it is possible to achieve both durability and flexibility in a high temperature environment due to repeated charge / discharge and heat generation, a long-life non-aqueous secondary battery with reduced discharge capacity reduction in the charge / discharge cycle is obtained. Can do.
  • the resin fine particles obtained by copolymerization of the body have the effect of improving the physical properties such as adhesion to the current collector, and the functional groups remain in the particles and on the surface even after the polymerization. Since aggregation may be prevented or particle stability after synthesis may be maintained, it can be preferably used.
  • a part of the carboxyl group, tertiary butyl group, sulfonic acid group, and phosphoric acid group may react during polymerization and be used for intra-particle crosslinking.
  • the total amount of ethylenically unsaturated monomers used in the emulsion polymerization (100% by weight in total) is 0.
  • the content is preferably 1 to 10% by weight, and more preferably 1 to 5% by weight.
  • the monomer containing these functional groups is less than 0.1% by weight, the stability of the particles may be deteriorated.
  • the content exceeds 10% by weight the hydrophilicity of the binder composition becomes too strong, and the electrolytic solution resistance may deteriorate.
  • these functional groups may react during drying and be used for cross-linking within or between particles.
  • carboxyl groups can react with epoxy groups during polymerization and drying to introduce a crosslinked structure into resin fine particles.
  • a tertiary butyl group can also react with an epoxy group in the same manner as described above because tertiary butyl alcohol is generated and a carboxyl group is formed when heat of a certain temperature or higher is applied.
  • These monomers (c7) are used in combination of two or more of the above-mentioned monomers in order to adjust the polymerization stability and glass transition temperature of the particles, as well as the film formability and film properties. Can be used. Further, for example, by using (meth) acrylonitrile in combination, there is an effect that rubber elasticity is exhibited.
  • the crosslinked resin fine particles can be synthesized by a conventionally known emulsion polymerization method.
  • emulsifier used in emulsion polymerization As the emulsifier used in the emulsion polymerization, conventionally known emulsifiers such as a reactive emulsifier having an ethylenically unsaturated group and a non-reactive emulsifier having no ethylenically unsaturated group can be arbitrarily used.
  • the reactive emulsifier having an ethylenically unsaturated group can be further roughly classified into anionic and nonionic nonionic ones. Especially when anionic reactive emulsifier or nonionic reactive emulsifier having an ethylenically unsaturated group is used, the dispersion particle size of the copolymer becomes finer and the particle size distribution becomes narrower, so it is used as a binder for secondary battery electrodes. In this case, the resistance to electrolytic solution can be improved.
  • anionic reactive emulsifiers or nonionic reactive emulsifiers having an ethylenically unsaturated group may be used singly or in combination.
  • anionic reactive emulsifier having an ethylenically unsaturated group are illustrated below, but usable emulsifiers are not limited thereto.
  • an alkyl ether type (commercially available products include, for example, Aqualon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Co., Ltd.
  • sulfosuccinic acid ester system for example, Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Elemiol manufactured by Sanyo Chemical Co., Ltd.) JS-2 etc.
  • alkyl phenyl ether type or alkyl phenyl ester type commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) , HS-10, HS-20, HS-30, ADEKA Corporation ADEKA Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.) (meth) acrylate sulfate ester (commercially available products include, for example, Japan Emulsifier Stock Company Antox MS-60
  • Nonionic reactive emulsifiers include, for example, alkyl ethers (for example, commercially available products such as Adeka Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation, LATEMUL PD- manufactured by Kao Corporation, etc.
  • alkylphenyl ethers or alkylphenyl esters commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) -50, Adeka Soap NE-10, NE-20, NE-30, NE-40, etc., manufactured by ADEKA Corporation; (meth) acrylate sulfate ester (commercially available products include, for example, RMA- manufactured by Nippon Emulsifier Co., Ltd.) 564, RMA-568, RMA-1114, etc.).
  • a non-reactive emulsifier having no ethylenically unsaturated group can be used in combination with the above-described reactive emulsifier having an ethylenically unsaturated group, if necessary.
  • Non-reactive emulsifiers can be broadly classified into non-reactive anionic emulsifiers and non-reactive nonionic emulsifiers.
  • non-reactive nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Sorbitan monolaurate, sorbitan monostearate, sorbitan higher fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; polyoxyethylene monolaurate, Polyoxyethylene higher fatty acid esters such as polyoxyethylene monostearate; oleic acid monoglyceride, stearic acid monog Glycerine higher fatty acid esters such as celite, polyoxyethylene-polyoxypropylene block copolymers, and the like can be exemplified polyoxyethylene distyrenated phenyl ether.
  • non-reactive anionic emulsifiers include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate; polyoxyethylene lauryl ether Polyoxyethylene alkyl ether sulfates such as sodium sulfate; polyoxyethylene alkylaryl ether sulfates such as polyoxyethylene nonylphenyl ether sodium sulfate; sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, polyoxyethylene lauryl sulfosuccinic acid Alkylsulfosuccinic acid ester salts such as sodium and their derivatives; polyoxyethylene distyrenated phenyl ether And the like can be exemplified Le sulfuric ester salts.
  • the amount of the emulsifier used is not necessarily limited, and can be appropriately selected according to physical properties required when the crosslinked resin fine particles are finally used as a binder for a secondary battery electrode.
  • the emulsifier is usually preferably 0.1 to 30 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the total of ethylenically unsaturated monomers. More preferably, it is in the range of 5 to 10 parts by weight.
  • a water-soluble protective colloid can be used in combination.
  • water-soluble protective colloids include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt; Examples thereof include saccharides, and these can be used alone or in a combination of plural kinds.
  • the amount of the water-soluble protective colloid used is 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight per 100 parts by weight of the total amount of ethylenically unsaturated monomers.
  • aqueous medium used in emulsion polymerization examples include water, and hydrophilic organic solvents can be used as long as the object of the present invention is not impaired.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization, and known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used.
  • the oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide.
  • Organic peroxides such as oxy-3,5,5-trimethylhexanoate and di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4- Examples thereof include azobis compounds such as dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobiscyclohexane-1-carbonitrile. These can be used alone or in combination of two or more. These polymerization initiators are preferably used in an amount of 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.
  • a water-soluble polymerization initiator is preferable.
  • ammonium persulfate, potassium persulfate, hydrogen peroxide, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, and the like which are conventionally known are preferably used.
  • Can do are preferably used.
  • a reducing agent when performing emulsion polymerization, can be used in combination with a polymerization initiator as desired. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature.
  • a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, Examples include reducing inorganic compounds such as sodium bisulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the total ethylenically unsaturated monomer.
  • the polymerization temperature is not less than the polymerization start temperature of each polymerization initiator.
  • the polymerization time is not particularly limited, but is usually 2 to 24 hours.
  • ⁇ Other materials used for reaction> sodium acetate, sodium citrate, sodium bicarbonate and the like as a buffering agent, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan as a chain transfer agent
  • a suitable amount of mercaptans such as t-dodecyl mercaptan can be used.
  • a monomer having an acidic functional group such as a carboxyl group-containing ethylenically unsaturated monomer
  • it may be neutralized with a basic compound before or after the polymerization.
  • a basic compound such as trimethylamine, triethylamine and butylamine
  • alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine and aminomethylpropanol
  • a base such as morpholine.
  • it is a highly volatile base that is highly effective in drying, and preferred bases are aminomethylpropanol and ammonia.
  • the glass transition temperature (hereinafter also referred to as Tg) of the crosslinked resin fine particles is preferably ⁇ 30 to 70 ° C., more preferably ⁇ 20 to 30 ° C.
  • Tg glass transition temperature
  • the glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).
  • Measurement of the glass transition temperature by DSC can be performed as follows. About 2 mg of resin obtained by drying the cross-linked resin fine particles is weighed on an aluminum pan, the test container is set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 10 ° C./min is read. The peak temperature at this time is defined as the glass transition temperature.
  • the particle structure of the crosslinked resin fine particles may be a multi-layer structure, so-called core-shell particles.
  • core-shell particles it is possible to localize a resin in which a monomer having a functional group is mainly polymerized in the core part or the shell part, or to provide a difference in Tg or composition between the core and the shell, thereby improving the curability and drying.
  • Property, film formability, and mechanical strength of the binder can be improved.
  • the average particle size of the crosslinked resin fine particles is preferably 10 to 500 nm, more preferably 30 to 250 nm, from the viewpoint of the binding property of the electrode active material and the stability of the particles. Further, when a large amount of coarse particles exceeding 1 ⁇ m are contained, the stability of the particles is impaired, so that the coarse particles exceeding 1 ⁇ m are preferably at most 5% by weight.
  • an average particle diameter represents a volume average particle diameter, and can be measured by the dynamic light scattering method.
  • the measurement of the average particle diameter by the dynamic light scattering method can be performed as follows.
  • the cross-linked resin fine particle dispersion is diluted with water 200 to 1000 times depending on the solid content.
  • About 5 ml of the diluted solution is injected into a cell of a measuring device [Microtrack manufactured by Nikkiso Co., Ltd.], and the measurement is performed after inputting the solvent (for example, water) and the refractive index condition of the resin according to the sample.
  • the peak of the volume particle size distribution data (histogram) obtained at this time is defined as the average particle size.
  • the binder composition further includes a non-crosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound. It is preferable to include at least one uncrosslinked compound (D) [hereinafter sometimes referred to as compound (D)].
  • the “uncrosslinked functional group-containing compound” which is the compound (D) is an internal cross-linked structure (three-dimensional cross-linked structure) of cross-linked resin fine particles as in the monomer group (C1). Unlike the compound to be formed, it refers to a compound which is added after the resin fine particles are subjected to emulsion polymerization (polymer formation) (does not participate in the internal cross-linking of the resin fine particles). That is, “uncrosslinked” means not involved in the formation of an internal crosslinked structure (three-dimensional crosslinked structure) of the crosslinked resin fine particles.
  • the cross-linked resin fine particles have a cross-linked structure, so that the electrolytic solution resistance is secured, and by using the compound (D), it is selected from an epoxy group, an amide group, a hydroxyl group, and an oxazoline group in the compound (D).
  • the at least one functional group may contribute to adhesion with the current collector or the electrode.
  • the binder composition for secondary battery electrodes excellent in flexibility can be obtained by adjusting the amount of the crosslinked structure and functional group.
  • the cross-linked resin fine particles need to be cross-linked inside the particles. Electrolytic solution resistance can be ensured by appropriately adjusting the crosslinking inside the particles. Furthermore, by adding the uncrosslinked compound (D) to the functional group-containing crosslinked resin fine particles, an epoxy group, an amide group, a hydroxyl group or an oxazoline group acts on the current collector, and adhesion to the current collector or the electrode. Can be improved effectively. Since the functional group contained in the compound (D) is stable by heat during long-term storage or electrode production, the effect of adhesion to the current collector is large even when used in a small amount. Furthermore, it is excellent in storage stability.
  • the compound (D) may react with the functional group in the cross-linked resin fine particles for the purpose of adjusting the flexibility and the electrolytic solution resistance of the binder. If the functional group in the compound (D) is excessively used for the reaction, the functional group capable of interacting with the current collector or the electrode is decreased. For this reason, the reaction between the crosslinked resin fine particles and the compound (D) needs to be at a level that does not impair the adhesion to the current collector or the electrode. Further, when a part of the functional group contained in the compound (D) is used for the crosslinking reaction [when the compound (D) is a polyfunctional compound], by adjusting the degree of crosslinking of these functional groups, It is possible to balance the resistance to electrolytic solution and the adhesion.
  • uncrosslinked epoxy group-containing compound examples include epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; Radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers containing monomers; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol Diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) Cyclohexane Poly
  • epoxy resins such as bisphenol A-epichlorohydrin type epoxy resins and bisphenol F-epichlorohydrin type epoxy resins, and ethylenically unsaturated monomers containing epoxy group-containing ethylenically unsaturated monomers.
  • a radical polymerization resin obtained by polymerizing a saturated monomer is preferred.
  • the epoxy resin can be expected to have a synergistic effect of improving the electrolytic solution resistance by having a bisphenol skeleton and improving the adhesion of the current collector by a hydroxyl group contained in the skeleton.
  • the radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an epoxy group-containing ethylenically unsaturated monomer has a higher adhesion to the current collector by having more epoxy groups in the resin skeleton.
  • it since it is a resin, an effect of improving the resistance to electrolytic solution can be expected as compared with the monomer.
  • Non-crosslinked amide group-containing compounds include, for example, primary amide group-containing compounds such as (meth) acrylamide; N-methylolacrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meta) ) Alkyrol (meth) acrylamide compounds such as acrylamide; N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meta ) Monoalkoxy (meth) acrylamide compounds such as acrylamide and N-pentoxymethyl- (meth) acrylamide; N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N -Di (Etoki Methyl) acrylamide, N-ethoxymethyl-N-propoxy
  • radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including amide group-containing ethylenically unsaturated monomers such as acrylamide are particularly preferable.
  • amide group-containing ethylenically unsaturated monomers such as acrylamide
  • uncrosslinked hydroxyl group-containing compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate 4-hydroxyvinylbenzene, Hydroxyl group-containing ethylenically unsaturated monomers such as 1-ethynyl-1-cyclohexanol and allyl alcohol; radical polymerization obtained by polymerizing ethylenically unsaturated monomers containing the hydroxyl group-containing ethylenically unsaturated monomers Resins: linear aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol; propylene glycol, neopenty
  • radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including a hydroxyl group-containing ethylenically unsaturated monomer or cyclic diols are particularly preferable.
  • the radical polymerization resin obtained by polymerizing ethylenically unsaturated monomers including hydroxyl group-containing ethylenically unsaturated monomers improves current collector adhesion by having more hydroxyl groups in the resin skeleton.
  • the resin can be expected to have an effect of improving the resistance to electrolytic solution compared to the monomer.
  • cyclic diols can be expected to have an effect of improving the resistance to electrolytic solution by having a cyclic structure in the skeleton.
  • Uncrosslinked oxazoline group-containing compound examples include 2′-methylenebis (2-oxazoline), 2,2′-ethylenebis (2-oxazoline), and 2,2′-ethylenebis (4-methyl-2-oxazoline).
  • oxazoline group-containing compounds in particular, phenylene bis-type oxazoline compounds such as 2′-p-phenylenebis (2-oxazoline), or ethylenically unsaturated monomers containing an oxazoline group-containing ethylenically unsaturated monomer A radical polymerization resin obtained by polymerizing is preferred.
  • the phenylenebis type oxazoline compound has an effect of improving the resistance to electrolytic solution by having a phenyl group in the skeleton.
  • a radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an oxazoline group-containing ethylenically unsaturated monomer has a current collector adhesion by having more oxazoline groups in the resin skeleton.
  • the resistance to an electrolytic solution can be improved as compared with a monomer.
  • Compound (D) is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the solid content of the binder composition (for example, crosslinked resin fine particles). .
  • the addition amount of the compound (D) is less than 0.1 parts by weight, the amount of the functional group contributing to the adhesion to the current collector decreases, and may not sufficiently contribute to the improvement in the adhesion to the current collector. is there.
  • the amount exceeds 50 parts by weight adverse effects on the binder performance such as leakage of the compound (D) into the electrolyte solution may occur.
  • two or more types of compounds (D) can be used in combination.
  • the molecular weight of the compound (D) is not particularly limited, but the weight average molecular weight is preferably 1,000 to 1,000,000, and more preferably 5,000 to 500,000. If the molecular weight is less than 1,000, the adhesion effect to the current collector may not be sufficient, and if the molecular weight exceeds 1,000,000, the viscosity of the compound may increase, The handling property may be deteriorated.
  • the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the compound (D) may be a compound that dissolves in a solvent or a compound that disperses.
  • the aqueous composition for forming a secondary battery electrode of the present invention can be used as a composite ink or a composition for forming a base layer.
  • a composite ink that essentially includes an active material, which is one of the preferred embodiments of the electrode forming composition.
  • the mixed ink includes positive electrode mixed ink or negative electrode mixed ink, and the mixed ink is composed of an electrode active material, a binder composition (C), a dispersant (A), and an aqueous liquid medium (E). Further, a carbon material which is a thickener and a conductive aid can be contained.
  • the positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to. Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V 2 O 5 , V 6 O 13 , TiO 2 , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc.
  • lithium and transition metals examples include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, transition metal sulfide powders such as TiS 2 and FeS, and the like.
  • conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used.
  • the negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions.
  • metal Li alloys thereof such as tin alloys, silicon alloys, lead alloys, etc., Li X Fe 2 O 3 , Li X Fe 3 O 4 , Li X WO 2 , lithium titanate, lithium vanadate, silicon
  • Metal oxides such as lithium oxide, conductive polymer such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers.
  • These negative electrode active materials can be used alone or in combination.
  • the size of these electrode active materials is preferably in the range of 0.05 to 100 ⁇ m, more preferably in the range of 0.1 to 50 ⁇ m.
  • the dispersed particle diameter of the electrode active material in the composite ink is preferably 0.5 to 20 ⁇ m.
  • the dispersed particle size referred to here is a particle size (D50) that is 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution.
  • a particle size distribution meter such as a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).
  • the composite ink preferably contains a carbon material in order to further increase the conductivity of the formed electrode.
  • the carbon material is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, conductive carbon fiber (carbon nanotube, carbon nanofiber, carbon fiber), fullerene, etc. alone Or two or more types can be used together. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.
  • Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material.
  • Ordinarily oxidized carbon black, hollow carbon and the like can also be used.
  • the oxidation treatment of carbon is performed by treating carbon at a high temperature in the air or by secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., for example, such as phenol group, quinone group, carboxyl group, carbonyl group.
  • This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon.
  • it since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.
  • the specific surface area (BET) determined from the adsorption amount of nitrogen is 20 m 2 / g or more and 1500 m 2 / g or less, preferably 50 m 2 / g or more and 1500 m 2 / g or less, more preferably 100 m 2. / G or more and 1500 m 2 / g or less are desirable.
  • BET specific surface area
  • the particle size of carbon black is preferably 0.005 to 1 ⁇ m in terms of primary particle size, and particularly preferably 0.01 to 0.2 ⁇ m.
  • the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.
  • the dispersed particle size of the carbon material, which is a conductive additive, in the mixed ink is refined to 0.03 ⁇ m or more and 5 ⁇ m or less. It may be difficult to produce a composition having a dispersed particle size of the carbon material as the conductive aid of less than 0.03 ⁇ m. In addition, when a composition having a dispersed particle diameter of the carbon material as the conductive auxiliary agent exceeding 2 ⁇ m is used, problems such as variations in the material distribution of the composite coating film and variations in the resistance distribution of the electrode may occur. .
  • the dispersed particle size referred to here is a particle size (D50) that is 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution.
  • a particle size distribution meter such as a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).
  • Examples of commercially available carbon black include Toka Black # 4300, # 4400, # 4500, # 5500 (Tokai Carbon Co., Furnace Black), Printex L and the like (Degussa Co., Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc., PUER BLACK100, 115, 205 etc. (Furnace Black, manufactured by Colombian), # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3030B, # 3030B # 3350B, # 3400B, # 5400B, etc.
  • conductive carbon fibers those obtained by firing from petroleum-derived raw materials are preferable, but those obtained by firing from plant-derived raw materials can also be used.
  • VGCF manufactured by Showa Denko Co., Ltd. manufactured with petroleum-derived raw materials can be mentioned.
  • aqueous liquid medium (E) As the aqueous liquid medium (E), it is preferable to use water. However, if necessary, for example, a liquid medium compatible with water may be used to improve the coating property to the current collector. good. Liquid media compatible with water include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid esters , Ethers, nitriles and the like, and may be used as long as they are compatible with water.
  • a film forming aid an antifoaming agent, a leveling agent, a preservative, a pH adjuster, a viscosity adjuster, and the like can be blended in the composite ink as necessary.
  • the viscosity of the composite ink is preferably 100 mPa ⁇ s or more and 30,000 mPa ⁇ s or less within a solid content of 30 to 90% by weight. Further, it is preferable that the active material is contained as much as possible within the viscosity range that can be applied.
  • the ratio of the active material to the solid content of the composite ink is preferably 80% by weight or more and 99% by weight or less.
  • the proportion of the dispersant (A) in the solid ink solid content is preferably 0.1 to 15% by weight.
  • the proportion of the carbon material in the solid material ink solid content is preferably 0.1 to 15% by weight.
  • the composite ink can be obtained by various methods. However, the use of a carbon material is optional.
  • a carbon material is optional.
  • a carbon material is optional.
  • a binder containing a carbon material and crosslinked resin fine particles in the aqueous dispersion A composition ink can be obtained by adding the composition (C).
  • the binder composition (C) containing the carbon material and the crosslinked resin fine particles can be added simultaneously, or after adding the carbon material, the binder may be added, or vice versa.
  • a composition ink can be obtained by adding the composition (C).
  • the active material and the binder can be added simultaneously, or after adding the active material, the binder composition (C) containing the crosslinked resin fine particles may be added, or vice versa.
  • the aqueous dispersion A carbon material can be added to the body to obtain a composite ink.
  • a dispersant (A), a binder composition (C) containing crosslinked resin fine particles and an aqueous liquid medium (E) After obtaining an aqueous dispersion of the active material containing the active material, the dispersant (A), the binder composition (C) containing the crosslinked resin fine particles and the aqueous liquid medium (E), the aqueous dispersion A carbon material can be added to the body to obtain a composite ink.
  • a mixture ink can be obtained by almost simultaneously mixing an active material, a carbon material, a dispersant (A), a binder composition (C) containing crosslinked resin fine particles and an aqueous liquid medium (E). .
  • the cellulosic thickener (B) may be added simultaneously with the dispersant (A) or may be added separately.
  • a disperser or a mixer which is usually used for pigment dispersion or the like can be used.
  • mixers such as dispersers, homomixers, or planetary mixers; homogenizers such as “Clairemix” manufactured by M Technique, or “Fillmix” manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru Enterprises "Dynomill”, etc.), Attritor, Pearl Mill (Eirich “DCP Mill”, etc.), or Coball Mill, etc .; Media type dispersers; Wet Jet Mill (Genus, “Genus PY”, Sugino Media-less dispersers such as “Starburst” manufactured by Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, or “MICROS” manufactured by Nara Machinery; or other roll mills, etc.
  • the present invention The present invention
  • a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating is preferably used.
  • the media it is preferable to use glass beads, ceramic beads such as zirconia beads or alumina beads.
  • a roll mill it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
  • a medialess disperser such as a roll mill or a homogenizer is preferable to a media type disperser.
  • the composition for forming an underlayer contains at least a conductive additive, a binder composition (C), a dispersant (A), and an aqueous liquid medium (E). Furthermore, a thickener (B) can also be used. About each component, it is the same as that of the case of compound ink.
  • the ratio of the carbon material as a conductive additive to the total solid content of the composition used for the electrode underlayer is preferably 5% by weight or more and 95% by weight or less, and more preferably 10% by weight or more and 90% by weight or less. If the carbon material that is the conductive auxiliary agent is small, the conductivity of the underlayer may not be maintained. On the other hand, if the carbon material that is the conductive auxiliary agent is too large, the resistance of the coating film may be reduced.
  • the appropriate viscosity of electrode base layer ink is based on the coating method of electrode base layer ink, generally it is preferable to set it as 10 mPa * s or more and 30,000 mPa * s or less.
  • the composite ink can be applied and dried on the current collector to form a composite layer, whereby a secondary battery electrode can be produced.
  • a composite material layer may be provided on the underlayer to produce a secondary battery electrode.
  • the composite layer provided on the underlayer may be formed using the above-described composite inks (1) to (4), or may be formed using other composite inks.
  • the material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries can be appropriately selected.
  • examples of the material for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel.
  • aluminum is particularly preferable as the positive electrode material
  • copper is preferable as the negative electrode material.
  • shape foil on a flat plate is generally used, but the surface is roughened, porous foam, perforated foil, and mesh current collector. Can also be used.
  • the method for applying the mixture ink on the current collector is not particularly limited, and a known method can be used. Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application
  • the thickness of the electrode mixture layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less. When the underlayer is provided, the thickness of the underlayer is generally 0.1 ⁇ m or more and 100 ⁇ m or less, preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
  • a secondary battery can be manufactured using the above electrode for at least one of a positive electrode and a negative electrode.
  • Secondary batteries include alkaline secondary batteries, lead-acid batteries, sodium-sulfur secondary batteries, lithium-air secondary batteries, etc., as well as lithium ion secondary batteries, which are conventionally known for each secondary battery. Electrolytic solutions, separators, and the like can be used as appropriate.
  • ⁇ Electrolyte> A case of a lithium ion secondary battery will be described as an example.
  • an electrolyte containing lithium dissolved in a non-aqueous solvent is used.
  • the electrolyte LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C , LiI, LiBr, LiCl, LiAlCl , LiHF 2, LiSCN, or LiBPh 4 etc. but are not limited to.
  • the non-aqueous solvent is not particularly limited.
  • carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ - Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2 -Grimes such as dibutoxyethane; esters such as methyl formate, methyl acetate and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. And the like.
  • These solvents may be used alone or in combination of two or more.
  • the electrolyte solution can be a polymer electrolyte that is held in a polymer matrix and made into a gel.
  • the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, and a polysiloxane having a polyalkylene oxide segment.
  • ⁇ Separator> examples of the separator include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.
  • the structure of the lithium ion secondary battery using the electrode forming composition of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, a paper type, a cylindrical type, Various shapes can be formed according to the purpose of use, such as a button type and a laminated type.
  • the weight average molecular weight of the anionic dispersant (A1-1) was about 20,000.
  • Binder composition (C1-4) A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a refluxing vessel was charged with 40 parts of ion-exchanged water and 0.2 part of ADEKA rear soap SR-10 (manufactured by ADEKA Corporation) as a surfactant.
  • the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 50%. An epoxy group-containing compound (methyl methacrylate / methyl acrylate / glycidyl methacrylate copolymer) solution was obtained. In addition, solid content was calculated
  • the contents of the dropping tanks 1 and 2 were dropped over 2 hours to carry out polymerization. After completion of dropping, stirring was continued for 1 hour while maintaining the internal temperature at 80 ° C. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C., and the solid content was 50%. A solution containing a hydroxyl group-containing compound (methyl methacrylate / butyl acrylate / 2-hydroxyethyl methacrylate copolymer) was obtained. In addition, solid content was calculated
  • CMC carboxymethyl cellulose, hydroxyl value: 415 to 500 mg KOH / g -HEC: hydroxyethyl cellulose, hydroxyl value: 600-720 mgKOH / g
  • Carbon material dispersion for secondary battery electrode 10 parts of acetylene black (DENKA BLACK HS-100) as a carbon material which is a conductive additive, and 10 parts of an aqueous dispersion or an aqueous dispersion of the anionic dispersant (A1-3) described in Synthesis Example 3 (2 parts as a solid content) ), 80 parts of water was mixed in a mixer, and further dispersed in a sand mill to obtain a carbon material dispersion (1) for a secondary battery electrode having a composition ratio shown in Table 4.
  • acetylene black DENKA BLACK HS-100
  • A1-3 anionic dispersant
  • Carbon material dispersions (2) to (29) for secondary battery electrodes were obtained in the same manner as the carbon material dispersion for secondary battery electrodes (1) with the formulation shown in Table 4.
  • the degree of dispersion of the carbon material dispersion for the secondary battery electrode was determined by judgment using a grind gauge (in accordance with JIS K5600-2-5). The evaluation results are shown in Table 4. The numbers in the table indicate the size of coarse particles. The smaller the value, the better the dispersibility and the more uniform secondary battery electrode forming composition.
  • Example 1 Secondary battery electrode by mixing 50 parts of carbon material dispersion for secondary battery electrode (1) (6 parts in solids) and binder composition (C1-4) in an amount of 4 parts by weight in solids A forming composition was obtained.
  • Examples 2 to 24, Comparative Examples 1 to 9 Compositions for forming secondary battery electrodes of Examples 2 to 24 and Comparative Examples 1 to 9 were prepared by mixing a carbon material dispersion for secondary battery electrodes and a binder composition so that the composition ratio shown in Table 5 was obtained. Got.
  • the evaluation of the electrolyte dissolution property was performed as follows.
  • the composition for forming a secondary battery electrode shown in Table 5 was applied on a 20 ⁇ m thick aluminum foil using a doctor blade, and then dried by heating under reduced pressure to form a coating film for forming a secondary battery electrode having a thickness of 5 ⁇ m. Produced.
  • the obtained coating film was immersed in a 1: 1 (volume ratio) non-aqueous electrolyte solvent of ethylene carbonate and diethyl carbonate, stored in a 60 ° C. environment for 3 days, and then the state of the coating film was observed.
  • the evaluation criteria are shown below, and the evaluation results are shown in Table 5. ⁇ : “No disintegration or peeling of coating film” ⁇ : “Partial disintegration and peeling of coating film are observed” ⁇ : “Most of the coating film is disintegrated and peeled”
  • Example 25 90 parts of LiCoO 2 as a positive electrode active material, 5 parts of an aqueous solution of a dispersant (A1-3) (1 part as a resin solid content), 8 parts (4 parts as a solid content) of a binder composition (C1-4) and water 43. Two parts were mixed to produce a positive electrode material ink for a secondary battery electrode having a solid content of 65% by weight.
  • the degree of dispersion of the composite ink was determined by judgment using a grind gauge (according to JIS K5600-2-5). The evaluation results are shown in Table 6A.
  • the numbers in the table indicate the size of the coarse particles. The smaller the value, the better the dispersibility and the more uniform the ink mixture for secondary battery electrodes.
  • this positive electrode secondary battery electrode composite ink was applied onto a 20 ⁇ m thick aluminum foil serving as a current collector using a doctor blade, and then dried under reduced pressure and dried to a thickness of 100 ⁇ m. It adjusted so that it might become. Furthermore, the rolling process by a roll press was performed and the positive electrode whose thickness is set to 80 micrometers was produced. The charge / discharge storage characteristics were evaluated using an evaluation coin type battery having a positive electrode as a working electrode and a metal lithium foil as a counter electrode.
  • Examples 26 to 40, Comparative Examples 10 to 25 For the secondary battery electrode for the positive electrode by changing the combination of the active material shown in Tables 6A and 6B, the carbon material as the conductive auxiliary agent, the carbon material dispersion, the composition for forming the secondary battery electrode, the dispersant and the binder composition. Except that water was added so that the final solid content of the composite ink was 65% by weight, a composite ink for a positive electrode for a positive electrode and a positive electrode were obtained and evaluated in the same manner as in Example 25. .
  • Example 41 95 parts of natural graphite as a negative electrode active material, 2.5 parts of an aqueous solution of a dispersant (A1-4) (0.5 parts as a resin solid content), 4 parts of a binder composition (C1-4) (2 parts as a solid content) And 93.5 parts of water were mixed to prepare a composite ink for a secondary battery electrode for a negative electrode having a solid content of 50% by weight.
  • the degree of dispersion of the composite ink was determined by judgment using a grind gauge. The evaluation results are shown in Table 6C.
  • the negative electrode secondary battery electrode composite ink was applied onto a copper foil having a thickness of 20 ⁇ m as a current collector using a doctor blade, and then dried by heating under reduced pressure to obtain an electrode thickness of 100 ⁇ m. It adjusted so that it might become. Furthermore, the rolling process by a roll press was performed, the negative electrode whose thickness was set to 80 micrometers was produced, and it evaluated similarly to the case of a positive electrode. The charge / discharge storage characteristics were evaluated using an evaluation coin-type battery having a negative electrode as a working electrode and a metal lithium foil as a counter electrode.
  • Examples 42 to 44, Comparative Examples 26 to 32 The active material shown in Table 6C, a carbon material as a conductive additive, a carbon material dispersion, a composition for forming a secondary battery electrode, a combination of a dispersant and a binder composition was changed, and a composite material for a secondary battery electrode for a negative electrode Except that water was added so that the final solid content of the ink was 50% by weight, a mixture ink for a secondary battery electrode for a negative electrode and a negative electrode were obtained and evaluated in the same manner as in Example 41.
  • Example 45 90 parts of LiCoO 2 as a positive electrode active material, 2.5 parts of an aqueous solution of a dispersing agent (A1-9) (0.5 part as a resin solid content), 33.3 parts of a 3% aqueous solution of CMC as a thickener (as a solid content) 1 part), 7 parts of binder composition (C1-6) (3.5 parts as a solid content) and 13.3 parts of water are mixed to obtain a composite material for a secondary battery electrode for a positive electrode having a solid content of 65% by weight. An ink was prepared. The composition is shown in Table 7A. Production and evaluation of the positive electrode were carried out in the same manner as in Example 25.
  • Examples 46 to 52, Examples 60 to 70, and Comparative Examples 33 to 40 The active material shown in Table 7A and Table 8A, the carbon material that is a conductive auxiliary agent, the carbon material dispersion, the composition for forming a secondary battery electrode, the dispersant, the thickener, and the binder composition are changed to be used for the positive electrode.
  • Example 45 In the same manner as in Example 45 except that water was added so that the final solid content of the secondary battery electrode mixture ink was 65% by weight, a positive electrode secondary battery electrode mixture ink and a positive electrode were obtained. , Evaluated in the same way.
  • Example 53 94 parts of natural graphite as a negative electrode active material, 2.5 parts of an aqueous solution of a dispersant (A1-3) (0.5 parts as a resin solid content), 5 parts of a binder composition (C1-4) (2.5 parts as a solid content) Part), 25 parts of a 2% aqueous solution of CMC as a thickener (0.5 part as a solid content) and 68.5 parts of water are mixed, and a composite material for a secondary battery electrode for a negative electrode having a solid content of 50% by weight.
  • An ink was prepared. The composition is shown in Table 7B. Production and evaluation of the negative electrode were carried out in the same manner as in Example 41.
  • Examples 54 to 59, Examples 71 to 76, Comparative Examples 41 to 43 The active material shown in Table 7B and Table 8B, the carbon material that is a conductive auxiliary agent, the carbon material dispersion, the composition for forming a secondary battery electrode, the dispersant, the thickener, and the binder composition are changed to be used for the negative electrode.
  • Example 53 In the same manner as in Example 53 except that water was added so that the final solid content of the secondary battery electrode composite ink was 50% by weight, a secondary battery electrode composite ink and negative electrode for negative electrode were obtained. , Evaluated in the same way.
  • Viscosity of compound ink To measure the viscosity of the slurry, a rheometer (“AR-G2” manufactured by TA Instruments) was used, and 0.01 (when the share rate was changed from 0.001 (1 / s) to 10 (1 / s). The viscosities of 1 / s) and 1 (1 / s) were determined.
  • the electrode produced above was formed into a strip shape and wound so that the current collector side was in contact with a metal rod having a diameter of 3 mm, and cracks on the electrode surface that occurred during winding were determined by visual observation. The one that does not crack is more flexible. ⁇ : “No cracks (a level where there is no practical problem)” ⁇ ⁇ : “In rare cases, cracks are seen (there is a problem, but the usable level)” ⁇ : “Partial cracks are seen” ⁇ : “Overall cracks are seen”
  • a coin-type battery comprising a non-aqueous electrolyte solution in which LiPF 6 was dissolved at a concentration of 1 M in a mixed solvent in which carbonate was mixed at a ratio of 1: 1 (volume ratio) was produced.
  • the coin-type battery was fabricated in a glove box substituted with argon gas.
  • the obtained coin-type battery was subjected to charge / discharge measurement using a charge / discharge device (SM-8 manufactured by Hokuto Denko).
  • SM-8 charge / discharge device
  • the active material to be used was LiFePO 4
  • constant current and constant voltage charging was continued to a charge end voltage of 4.5 V at a charging current of 1.0 C.
  • constant current discharge was performed at a discharge current of 1.0C until the discharge end voltage of 2.0V was reached.
  • These charging / discharging cycles were taken as one cycle, and 100 cycles of charging / discharging were repeated.
  • the discharge capacity at the third cycle was defined as the initial discharge capacity (the initial discharge capacity was set to 100% discharge capacity retention rate), and the discharge capacity retention rate after 100 cycles was calculated (the closer to 100%, the better).
  • ⁇ “Change rate is 95% or more. Particularly excellent.” ⁇ ⁇ : “Change rate is 90% or more and less than 95%. No problem at all” ⁇ : “Change rate is 85% or more and less than 90%. ⁇ : “Change rate is less than 85%.
  • the carbon material that is the active material or conductive aid is insufficiently dispersed in the composite ink, a uniform conductive network is not formed when it is used as an electrode. It is considered that the resulting resistance distribution occurs and current concentration occurs when used as a battery, thereby causing deterioration.
  • the dispersion control of the carbon material or the active material, which is a conductive auxiliary agent is insufficient, that is, when an anionic dispersant is not used or an anionic dispersant does not fall within the scope of the present invention, In the case where is used, there is a tendency that the coating film characteristics and battery characteristics of the electrode are insufficient. In particular, when the dispersion control of the carbon material that is a conductive additive is insufficient, the tendency is remarkable.
  • the resistance of the electrode coating film to the electrolytic solution is further improved by combining a dispersant and a binder composition (particularly, a binder composition containing a crosslinkable resin fine particle aqueous dispersion).
  • Example 77 and 78, Comparative Example 44 The composition for forming a secondary battery electrode shown in Table 9 was applied onto a 20 ⁇ m-thick aluminum foil serving as a current collector using a doctor blade, and then dried by heating, so that the base layer was 5 ⁇ m in thickness. Formed. Subsequently, after applying the mixed ink for secondary battery positive electrode shown in Table 6A on the underlayer, it was dried by heating under reduced pressure to obtain a positive electrode in the same manner as in Example 25 and evaluated in the same manner.

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Abstract

L'invention concerne une composition aqueuse pour former une électrode d'accumulateur, contenant une matière active d'électrode et/ou une matière carbonée servant d'auxiliaire de conduction, un dispersant anionique (A), et de l'eau, le dispersant anionique (A) comprenant de l'acide carboxylique et/ou de l'acide sulfonique au niveau de sites anioniques, l'indice d'acidité étant compris entre 100 et 600 mg KOH/g, l'indice hydroxyle étant compris entre 0 et 400 mg KOH/g, et la masse moléculaire moyenne en poids étant d'au moins 5000, ce qui permet de former un accumulateur présentant une excellente aptitude à disperser la matière active et l'auxiliaire de conduction, et d'excellentes caractéristiques de cycle de charge-décharge.
PCT/JP2012/057143 2011-03-31 2012-03-21 Composition aqueuse pour former une électrode d'accumulateur, électrode d'accumulateur et accumulateur associés WO2012133030A1 (fr)

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JP2013145763A (ja) * 2013-04-30 2013-07-25 Nippon Zeon Co Ltd 二次電池多孔膜用スラリー組成物、二次電池用電極、二次電池用セパレータおよび二次電池
JP2014107073A (ja) * 2012-11-27 2014-06-09 Toyo Ink Sc Holdings Co Ltd 非水系二次電池電極形成用導電性プライマー組成物、それを用いた非水系二次電池電極、及び非水系二次電池
JP2014120411A (ja) * 2012-12-19 2014-06-30 Toyo Ink Sc Holdings Co Ltd 二次電池電極形成用組成物、二次電池電極、及び二次電池
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