WO2014156195A1 - Composition de liant pour électrodes de batterie secondaire, son procédé de fabrication, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires, et batterie secondaire - Google Patents

Composition de liant pour électrodes de batterie secondaire, son procédé de fabrication, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires, et batterie secondaire Download PDF

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Publication number
WO2014156195A1
WO2014156195A1 PCT/JP2014/001852 JP2014001852W WO2014156195A1 WO 2014156195 A1 WO2014156195 A1 WO 2014156195A1 JP 2014001852 W JP2014001852 W JP 2014001852W WO 2014156195 A1 WO2014156195 A1 WO 2014156195A1
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secondary battery
monomer
binder composition
mass
parts
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PCT/JP2014/001852
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English (en)
Japanese (ja)
Inventor
鍵 王
豊 丸橋
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日本ゼオン株式会社
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Priority to CN201480016769.0A priority Critical patent/CN105074977B/zh
Priority to JP2015508095A priority patent/JP6206484B2/ja
Publication of WO2014156195A1 publication Critical patent/WO2014156195A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a binder composition for a secondary battery electrode and a manufacturing method thereof, a slurry composition for a secondary battery electrode, an electrode for a secondary battery, and a secondary battery.
  • Secondary batteries especially lithium ion secondary batteries, are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications.
  • the battery members such as the electrodes (positive electrode and negative electrode) of the secondary battery are obtained by binding the components contained in these battery members or the components and a substrate (for example, a current collector) with a binder.
  • a substrate for example, a current collector
  • a binder for example, a current collector
  • an electrode of a secondary battery usually includes a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer is formed by, for example, applying an electrode slurry composition in which an electrode active material and a binder composition are dispersed in a dispersion medium on a current collector, and drying the electrode active material and the like with a binder. It is formed by binding.
  • attempts have been made to improve the binder composition and slurry composition used for forming these battery members in order to achieve further performance improvement of the secondary battery.
  • Patent Documents 1 to 3 it has been proposed to use a binder composition containing a specific copolymer for the production of a secondary battery electrode (see, for example, Patent Documents 1 to 3).
  • the binder composition described in Patent Document 1 it contains a copolymer having specific properties obtained by emulsion polymerization of styrene, an ethylenically unsaturated carboxylic acid ester, an ethylenically unsaturated carboxylic acid, and an internal crosslinking agent. Therefore, the active material and the active material and the current collector can be satisfactorily bound in an aqueous dispersion, and by using such a binder composition, a lithium ion secondary battery excellent in charge / discharge high temperature cycle characteristics Can be provided.
  • the binder composition described in Patent Document 2 contains a copolymer of an acrylate ester or a methacrylic ester and an ⁇ , ⁇ -unsaturated nitrile compound.
  • An excellent positive electrode can be provided.
  • a predetermined ⁇ , ⁇ -ethylenically unsaturated nitrile compound such as acrylonitrile is polymerized, and then a predetermined ethylenically unsaturated carboxylic acid such as 2-ethylhexyl acrylate is used. Since a copolymer (multistage polymer) obtained by adding and polymerizing an ester or the like is contained, a positive electrode excellent in binding power and flexibility can be provided.
  • JP 2011-243464 A International Publication No. 2006/038652 Japanese Patent No. 4736804
  • the present invention can provide a secondary battery that has excellent high-temperature storage characteristics and high-temperature cycle characteristics, in which generation of gas due to residual monomers is suppressed, and is excellent in stability over time.
  • An object is to provide a binder composition.
  • an object of this invention is to provide the slurry composition for secondary battery electrodes using the said binder composition.
  • an object of this invention is to provide the electrode for secondary batteries using the said slurry composition for secondary battery electrodes.
  • Another object of the present invention is to provide a secondary battery using the secondary battery electrode, which has excellent high-temperature storage characteristics and high-temperature cycle characteristics and reduced gas generation.
  • a polymer is prepared once, and then a polymerization initiator such as persulfate is further added to further advance the polymerization reaction (that is, the residual monomer is polymerized). It is also conceivable to reduce the amount of residual monomer containing a (meth) acrylic acid ester monomer at or above.
  • a polymerization initiator was further added and the polymerization reaction proceeded, a large amount of the residue of the polymerization initiator such as persulfate was present in the binder composition or the secondary. It became clear that the electrical characteristics of the secondary battery might be deteriorated due to inclusion in the battery.
  • the present inventors conducted further intensive studies for the purpose of solving the above problems. And the present inventors polymerize the residual monomer by reducing the amount of residual monomer without using a large amount of peroxide by performing redox polymerization using a reductone compound after preparing a polymer once. I was inspired by that. Furthermore, the inventors of the present invention also provide a secondary battery electrode binder composition containing a particulate polymer prepared using a (meth) acrylate monomer, and a (meth) acrylate ester having a boiling point of 145 ° C. or higher.
  • the present invention aims to advantageously solve the above problems, and the binder composition for a secondary battery electrode of the present invention comprises at least one of a particulate polymer, a reductone compound and an oxidant thereof.
  • the water-containing particulate polymer is obtained by polymerizing a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher, and the (meth) acrylic acid having a boiling point of 145 ° C. or higher.
  • the content ratio of the ester monomer is 1 ⁇ 10 ⁇ 6 parts by mass to 1500 ⁇ 10 ⁇ 6 parts by mass with respect to 100 parts by mass of the particulate polymer.
  • the binder composition for secondary battery electrodes is formed by using a reductone compound and limiting the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher to a predetermined range.
  • the secondary battery obtained by using such a binder composition for a secondary battery electrode it is possible to suppress the generation of gas due to the residual monomer.
  • the said binder composition for secondary battery electrodes is used, the secondary battery which has a favorable high temperature storage characteristic and a high temperature cycling characteristic can be provided.
  • At least one of the reductone compound and its oxidant is selected from (iso) ascorbic acid and its salt, and their oxidant. It is preferable that This is because (iso) ascorbic acid and salts thereof, and oxidants thereof have little influence on battery characteristics and lead to improvement of slurry stability.
  • the content ratio of at least one of the reductone compound and its oxidant is 0.05 parts by mass or more and 5 parts by mass per 100 parts by mass of the particulate polymer.
  • the following is preferable.
  • the content of at least one of a reductone compound and its oxidant while sufficiently reducing the amount of residual monomer such as a (meth) acrylate monomer having a boiling point of 145 ° C. or higher in the binder composition for secondary battery electrodes As a result, the electrical characteristics of the secondary battery produced using the binder composition for secondary battery electrodes deteriorated, and at least one of the reductone compound and its oxidant remaining in the binder composition was decomposed. This is because the generation of gas in the secondary battery can be suppressed.
  • the monomer mixture preferably further contains a crosslinkable monomer.
  • the degree of swelling of the electrode formed using the binder composition for a secondary battery electrode with respect to the electrolyte solution is set to an appropriate level, and the high-temperature storage characteristics and high temperature of a lithium ion secondary battery produced using such a binder composition This is because the cycle characteristics can be improved.
  • the monomer mixture further contains 5 to 35% by mass of a (meth) acrylonitrile monomer. This is because the peel strength of the electrode mixture layer formed using the binder composition for secondary battery electrodes can be improved, and the degree of swelling with respect to the electrolytic solution can be made moderate.
  • the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is preferably 2-ethylhexyl acrylate. Since a polymer obtained using 2-ethylhexyl acrylate has high electrochemical stability and flexibility, current collection of an electrode mixture layer obtained using a binder composition for a secondary battery electrode blended with such a polymer. This is because the adhesion strength to the body can be improved, and as a result, the battery characteristics of the secondary battery having such an electrode mixture layer can be improved.
  • the manufacturing method of the binder composition for secondary battery electrodes of this invention is (meth) acrylic acid ester single-piece
  • a step (2) of 1 ⁇ 10 ⁇ 6 parts by mass to 1500 ⁇ 10 ⁇ 6 parts by mass with respect to 100 parts by mass of the combined product a step (2) of 1 ⁇ 10 ⁇ 6 parts by mass to 1500 ⁇ 10 ⁇ 6 parts by mass with respect to 100 parts by mass of the combined product .
  • the slurry composition for secondary battery electrodes of this invention is the binder composition and electrode for any of the above-mentioned secondary battery electrodes. It is characterized by containing an active material.
  • Such a slurry composition for a secondary battery electrode is excellent in stability over time, and when such a slurry composition for a secondary battery electrode is used, generation of gas due to residual monomers is suppressed, and good high-temperature storage characteristics and A secondary battery having high-temperature cycle characteristics can be provided.
  • the electrode for secondary batteries of this invention apply
  • the secondary battery of this invention is equipped with a positive electrode, a negative electrode, electrolyte solution, and a separator, and at least one of the said positive electrode and the said negative electrode is The electrode for a secondary battery described above.
  • Such a secondary battery has excellent high-temperature storage characteristics and high-temperature cycle characteristics, and gas generation is suppressed.
  • ADVANTAGE OF THE INVENTION According to this invention, generation
  • a binder composition can be provided.
  • the slurry composition for secondary battery electrodes using the said binder composition can be provided.
  • the electrode for secondary batteries using the said slurry composition for secondary battery electrodes can be provided.
  • the binder composition for secondary battery electrodes of the present invention is used when forming an electrode of a secondary battery.
  • the slurry composition for secondary battery electrodes of this invention is prepared including the binder composition for secondary battery electrodes of this invention, and an electrode active material.
  • the manufacturing method of the binder composition for secondary battery electrodes of this invention can be used when manufacturing the binder composition for secondary battery electrodes of this invention.
  • the secondary battery electrode of the present invention can be produced using the slurry composition for the secondary battery electrode of the present invention, and the lithium ion secondary battery of the present invention is the secondary battery electrode of the present invention. It is characterized by using.
  • the binder composition for secondary battery electrodes of the present invention is an aqueous binder composition using water as a dispersion medium, and includes at least one of a particulate polymer, a reductone compound, and an oxidant thereof.
  • the particulate polymer is a particulate polymer produced by polymerizing a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher.
  • the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is 1 ⁇ 10 ⁇ 6 mass relative to 100 mass parts of the particulate polymer.
  • the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher contained in the binder composition of the present invention is a polymerization of a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher.
  • “(meth) acryl” refers to acryl and / or methacryl.
  • the component contained in the electrode mixture layer (for example, the electrode active material) is produced from the electrode in the manufactured electrode. It is a component that can be held so as not to be detached.
  • a particulate polymer to be blended in the binder composition a particulate polymer produced by polymerizing a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher described below is used. be able to.
  • a particulate polymer is produced
  • the binder composition of the present invention is used for forming a positive electrode (secondary battery positive electrode binder composition)
  • the particulate polymer is an ⁇ , ⁇ -unsaturated nitrile monomer such as a (meth) acrylonitrile monomer.
  • (meth) acrylonitrile refers to acrylonitrile and / or methacrylonitrile.
  • the monomer mixture used when polymerizing the particulate polymer contains a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher.
  • the electrochemical stability and flexibility of the particulate polymer obtained by polymerizing the monomer mixture can be enhanced.
  • the adhesive strength of the electrode compound layer using a binder composition can be raised and the peel strength of an electrode can be improved, the battery characteristic of a secondary battery can be improved.
  • examples of the (meth) acrylic acid ester monomer include compounds represented by the formula (I): CH 2 ⁇ CR 1 —COOR 2 .
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group, a cycloalkyl group, or a functional group in which a part thereof is substituted.
  • Examples of (meth) acrylate monomers having a boiling point of 145 ° C. or higher include n-butyl acrylate (BA), n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate.
  • acrylates such as 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, hexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, and benzyl acrylate; n-butyl methacrylate, methacrylic acid Isobutyl, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stear methacrylate Le, and the like methacrylates such as benzyl methacrylate.
  • These monomers may be used individually by 1 type, and may be used in combination of 2 or more types.
  • acrylate is preferable, 2-ethylhexyl acrylate and n-butyl acrylate are preferable in terms of improving the peel strength of the secondary battery electrode, and 2-ethylhexyl acrylate is particularly preferable.
  • 2-ethylhexyl acrylate has a long side chain and reduces Tg of a polymer having monomer units derived from 2-ethylhexyl acrylate to improve flexibility and to improve electrochemical stability
  • a polymer Improved the adhesion strength of the electrode mixture layer obtained by using the binder composition for secondary battery electrodes blended with the current collector, and thus the battery characteristics of the secondary battery using the electrode having the electrode mixture layer It is because it can improve.
  • the boiling point of the (meth) acrylic acid ester monomer can be measured according to JIS K2254.
  • the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is preferably 10% by mass or more, more preferably 15% by mass in the monomer mixture. % Or more, still more preferably 30% by mass or more, particularly preferably 50% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less.
  • the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher in the monomer mixture 10% by mass or higher, flexibility is provided to the negative electrode mixture layer formed using the binder composition. be able to.
  • the peel strength of the negative electrode mixture layer formed using the binder composition can be improved by setting the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher to 70% by mass or less. .
  • the content rate of the (meth) acrylic acid ester monomer with a boiling point of 145 degreeC or more mentioned above in a monomer mixture Preferably it is 60 mass% or more, More preferably 65% by weight or more, still more preferably 70% by weight or more, particularly preferably 75% by weight or more, and preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less, particularly preferably Is 83 mass% or less.
  • the polymer is prevented from excessive swelling with respect to the electrolyte solution, and the binder
  • the peel strength of the positive electrode mixture layer formed using the composition can be improved, and the flexibility of the positive electrode mixture layer can be improved to make the positive electrode having the positive electrode mixture layer difficult to break.
  • the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher to 95% by mass or less the polymer is appropriately swollen with respect to the electrolytic solution, and the binder composition is used. An increase in electrical resistance of a secondary battery including the positive electrode formed in this manner can be suppressed, and the mechanical strength of the particulate polymer can be maintained and adhesion can be maintained.
  • the boiling point of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is preferably 150 ° C. or higher and 250 ° C. or lower.
  • High-boiling point (meth) acrylate monomer units generally have long side chains, and polymers comprising such monomer units are rich in flexibility and have good binding properties. This is because the battery characteristics of a secondary battery produced using a binder composition containing such a polymer can be improved.
  • Crosslinking monomer When using a binder composition for formation of a negative electrode, it is preferable that the monomer mixture used when superposing
  • the crosslinkable monomer is a monomer having the following crosslinkable group.
  • the crosslinkable group a heat crosslinkable group that usually causes a crosslinking reaction by heat is used.
  • the crosslinkable group include an epoxy group, an N-methylolamide group, an oxazoline group, and an allyl group.
  • the crosslinkable group and the crosslinking density can be easily adjusted.
  • a methylolamide group, an epoxy group, and an allyl group are preferred.
  • the higher the crosslinking density the lower the degree of swelling of the particulate polymer with respect to the electrolytic solution. Therefore, the degree of swelling of the particulate polymer can be controlled by adjusting the crosslinking density.
  • the kind of crosslinkable group may be one kind, and may be two or more kinds.
  • a crosslinkable monomer shall not be contained in the (meth) acrylic acid ester monomer mentioned above.
  • the monomer containing an epoxy group include a monomer containing a carbon-carbon double bond and an epoxy group, a monomer containing a halogen atom and an epoxy group, and the like.
  • Examples of the monomer containing a carbon-carbon double bond and an epoxy group include unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether; butadiene monoepoxide, Diene or polyene monoepoxides such as chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene; Alkenyl epoxides such as epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl-4-he
  • Examples of the monomer having a halogen atom and an epoxy group include epihalohydrin such as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, ⁇ -methylepichlorohydrin; p-chlorostyrene oxide; dibromo Phenyl glycidyl ether; and the like.
  • Examples of the monomer containing an N-methylolamide group include (meth) acrylamides having a methylol group such as N-methylol (meth) acrylamide.
  • Examples of the monomer containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl- Examples include 2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like.
  • Examples of the monomer containing an allyl group include allyl acrylate and allyl methacrylate.
  • crosslinkable monomer allyl acrylate or allyl methacrylate is preferable from the viewpoint of improvement in crosslink density and high copolymerizability.
  • the content of the crosslinkable monomer is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, particularly preferably 1% by mass or more, preferably 5% by mass in the monomer mixture. Hereinafter, it is more preferably 3% by mass or less, particularly preferably 2% by mass or less.
  • the degree of swelling in the electrolytic solution is set to an appropriate level, and the binder composition obtained using such a monomer mixture is used. This is because the high-temperature storage characteristics and high-temperature cycle characteristics of the secondary battery can be improved. Moreover, it is because the softness
  • Aromatic vinyl monomer When the binder composition is used for forming the negative electrode, the monomer mixture used for polymerizing the particulate polymer is styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, It is preferable to further contain a styrene monomer such as vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene, divinyl benzene and the like. Of these, styrene is preferably used as the aromatic vinyl monomer.
  • these may be used individually by 1 type and may be used in combination of 2 or more types.
  • an aromatic vinyl monomer such as a styrene monomer
  • the Tg of the polymer having monomer units derived from the aromatic vinyl monomer is increased, and the polymer strength of the particulate polymer is increased, As a result, the peel strength of the negative electrode mixture layer can be improved.
  • an aromatic vinyl monomer such as a styrene monomer
  • the ⁇ electron of the aromatic ring introduced into the particulate polymer contained in the binder composition and the aromatic of the carbon-based negative electrode active material. This is because the dispersibility of the conductive material can be improved by the interaction with the ⁇ electrons of the group ring.
  • the blending amount of the aromatic vinyl monomer such as the styrene monomer is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 80% by mass in the monomer mixture.
  • it is more preferably 70% by mass or less, particularly preferably 60% by mass or less.
  • the monomer mixture used when polymerizing the particulate polymer preferably further contains a monomer containing an acidic group (hereinafter sometimes referred to as “acidic group-containing monomer”).
  • a monomer unit containing an acidic group (hereinafter sometimes referred to as an “acidic group-containing monomer unit”) is particulate. It can be introduced into the polymer.
  • the acidic group include a carboxylic acid group (—COOH), a sulfonic acid group (—SO 3 H), and a phosphoric acid group (—PO 3 H 2 ).
  • the acidic group-containing monomer may have one acidic group or two or more acidic groups.
  • the number of acidic groups which the monomer containing an acidic group has may be one, and two or more may be sufficient as it.
  • the monomer containing a carboxylic acid group a monomer having a carboxylic acid group and a polymerizable group is usually used.
  • the monomer containing a carboxylic acid group include an unsaturated carboxylic acid monomer.
  • the unsaturated carboxylic acid monomer is a monomer having a carbon-carbon unsaturated bond and having a carboxylic acid group.
  • Examples of the unsaturated carboxylic acid monomer include unsaturated monocarboxylic acid and derivatives thereof; unsaturated dicarboxylic acid and acid anhydrides and derivatives thereof; and the like.
  • unsaturated monocarboxylic acids include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid.
  • unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, and ⁇ -Derivatives of ethylenically unsaturated monocarboxylic acids, such as diaminoacrylic acid.
  • unsaturated dicarboxylic acids include ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid.
  • unsaturated dicarboxylic acid anhydrides include ethylenically unsaturated dicarboxylic acid anhydrides such as maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • Examples of derivatives of unsaturated dicarboxylic acids include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, methylallyl maleate; and diphenyl maleate, nonyl maleate, maleate Examples thereof include maleate esters such as decyl acid, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleate.
  • Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid. In the present specification, “(meth) allyl” means allyl and / or methallyl.
  • Monomers having a phosphoric acid group include phosphoric acid-2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl phosphate- (meth) acryloyloxyethyl phosphate, ethylene phosphate And methacrylate.
  • acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and ethylene methacrylate phosphate are preferable.
  • unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and ethylenically unsaturated dicarboxylic acids such as itaconic acid are preferred. This is because the storage stability of the binder composition can be improved by further increasing the dispersibility of the particulate polymer in water.
  • the compounding amount of the acidic group-containing monomer is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, preferably 8% by mass in the monomer mixture. % Or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less.
  • the monomer mixture used for polymerizing the particulate polymer in the present invention is not limited to those described above unless the present invention is significantly impaired. May contain body.
  • These arbitrary monomers are monomers copolymerizable with the above-mentioned monomers.
  • Examples of monomers copolymerizable with the above-mentioned monomers include amide monomers such as acrylamide; olefins such as ethylene and propylene; diene monomers such as butadiene and isoprene; vinyl chloride; Monomers containing halogen atoms such as vinylidene chloride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; methyl vinyl ketone and ethyl vinyl Vinyl ketones such as ketone, butyl vinyl ketone, hexyl vinyl ketone and isopropenyl vinyl ketone; heterocyclic compounds containing a heterocyclic ring such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole; methyl (meth) acrylate, ethyl (meth) acrylate, propy
  • an ⁇ , ⁇ -unsaturated nitrile monomer and an acidic group-containing monomer can be suitably blended in the monomer mixture used for the polymerization of the particulate polymer.
  • the body is described in detail.
  • the monomer mixture used for polymerizing the particulate polymer further contains an ⁇ , ⁇ -unsaturated nitrile monomer such as a (meth) acrylonitrile monomer. It is preferable. This is because the use of an ⁇ , ⁇ -unsaturated nitrile monomer such as a (meth) acrylonitrile monomer can increase the binding strength of the binder composition and can significantly improve the strength of the positive electrode.
  • Examples of the ⁇ , ⁇ -unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like. Among these, acrylonitrile and methacrylonitrile are preferable and acrylonitrile is particularly preferable from the viewpoint of improving mechanical strength and binding properties. In addition, these may be used individually by 1 type and may be used in combination of 2 or more types.
  • the blending amount of the ⁇ , ⁇ -unsaturated nitrile monomer such as (meth) acrylonitrile monomer is preferably 1 to 50% by mass, more preferably 5 to 35% by mass in the monomer mixture. is there.
  • the content of an ⁇ , ⁇ -unsaturated nitrile monomer such as a (meth) acrylonitrile monomer is less than 1% by mass, the Tg of the particulate polymer is lowered, and the binder composition containing such a particulate polymer There is a possibility that the peel strength of the positive electrode mixture layer formed using the product may be lowered. Furthermore, in this case, the particulate polymer is likely to swell excessively with respect to the electrolytic solution, which may cause a decrease in peel strength.
  • a secondary material produced using such a binder composition with an appropriate value for the degree of swelling of the particulate polymer with respect to the electrolyte while improving the peel strength of the positive electrode produced using the binder composition containing the particulate polymer An increase in the internal resistance of the battery can be suppressed.
  • polymerizing a particulate polymer further contains an acidic group containing monomer.
  • the acidic group-containing monomer those described above in the section of “Monomer used for polymerization of particulate polymer in binder composition for negative electrode” can be used.
  • the blending amount in the monomer mixture is the same.
  • the monomer mixture used when polymerizing the particulate polymer in the present invention is not limited to those described above unless the present invention is significantly impaired. May contain body.
  • These arbitrary monomers are monomers copolymerizable with the above-mentioned monomers. Examples of monomers copolymerizable with the above-described monomers include styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl.
  • Styrene monomers such as styrene, ⁇ -methylstyrene and divinylbenzene; Amide monomers such as acrylamide; Olefins such as ethylene and propylene; Diene monomers such as butadiene and isoprene; Vinyl chloride and vinylidene chloride Halogen atom-containing monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone, Butyl vinyl keto , Vinyl ketones such as hexyl vinyl ketone and isopropenyl vinyl ketone; heterocycle-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (
  • the particulate polymer has a crosslinked structure.
  • the cross-linked structure can be formed by introducing the cross-linked monomer into the particulate polymer.
  • the particulate polymer may have a crosslinked structure.
  • a method for introducing a cross-linked structure for example, a method of incorporating a cross-linkable group by polymerizing a polymer from a monomer composition containing the above cross-linkable monomer, a combination of a polymer and a cross-linking agent And the method used.
  • the polymer can be crosslinked by irradiation with heat or energy rays.
  • the degree of crosslinking can be adjusted by the intensity of heating or irradiation with energy rays. Since the degree of swelling decreases as the degree of crosslinking increases, the degree of swelling of the particulate polymer can be controlled by adjusting the degree of crosslinking.
  • the weight average molecular weight of the particulate polymer is preferably 10,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, more preferably 500,000 or less.
  • the weight average molecular weight of the particulate polymer can be determined as a value in terms of polystyrene using tetrahydrofuran as a developing solvent by gel permeation chromatography (GPC).
  • the glass transition temperature (Tg) of the particulate polymer is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C.
  • the glass transition temperature of the particulate polymer is in the above range, a secondary battery electrode having excellent strength and flexibility can be obtained, and a secondary battery having high output characteristics can be obtained.
  • the glass transition temperature of the particulate polymer can be adjusted by combining various monomers.
  • the particulate polymer is insoluble in water. Therefore, the particulate polymer is usually in the form of particles in the binder composition and the slurry composition for secondary battery electrodes containing the binder composition, and is included in the secondary battery electrode while maintaining the particle shape. It is.
  • the particulate polymer being “water-insoluble” means that when 0.5 g of the compound is dissolved in 100 g of water at 25 ° C., the insoluble content becomes 90% by mass or more.
  • the volume average particle diameter of the particulate polymer is usually 0.001 ⁇ m or more, preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and usually 100 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less. is there.
  • the binder composition can exhibit an excellent binding force even when used in a small amount.
  • the volume average particle diameter is measured using a light scattering particle diameter measuring instrument.
  • the shape of the particles may be either spherical or irregular.
  • a particulate polymer may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the proportion of the particulate polymer in the solid content of the binder composition is usually 50% by mass or more, and preferably 70% by mass or more.
  • the “reductone compound” contained in the binder composition for a secondary battery electrode of the present invention refers to a compound having a R 3 C (OH) ⁇ C (OH) C ( ⁇ O) R 4 structure and a salt thereof. .
  • R 3 and R 4 may each be an independent organic group, or may together form a ring structure.
  • Examples of the compound having the R 3 C (OH) ⁇ C (OH) C ( ⁇ O) R 4 structure include glucic acid and its derivatives, reductic acid and its derivatives, ascorbic acid and its isomers, derivatives and the like. It is done.
  • the reductone compound is included in the form of an oxidant (deprotonated reductone; a compound having a R 3 C ( ⁇ O) C ( ⁇ O) C ( ⁇ O) R 4 structure and a salt thereof). Also good. Among these, at least one selected from ascorbic acid and its isomers, derivatives, salts thereof, and oxidants thereof is preferable because of low cost, toxicity, and environmental burden and high human safety.
  • Ascorbic acid (vitamin C) and its isomers and derivatives include, for example, D- or L-ascorbic acid and its sugar derivatives (for example, ⁇ -lactoascorbic acid, glucoascorbic acid, fucoscorbic acid, glucoheptascorbic acid, Maltoascorbic acid), isoascorbic acid (or L-erythroascorbic acid), also called erythorbic acid, enediol type ascorbic acid, enaminol type ascorbic acid, thioenolic type ascorbic acid, and ascorbyl palmitate.
  • D- or L-ascorbic acid and its sugar derivatives for example, ⁇ -lactoascorbic acid, glucoascorbic acid, fucoscorbic acid, glucoheptascorbic acid, Maltoascorbic acid
  • isoascorbic acid (or L-erythroascorbic acid) also called erythorbic acid,
  • ascorbic acid (vitamin C) and isomers and derivatives thereof include salts of the above-described compounds (for example, alkali metal salts, ammonium salts or salts known in the art), such as sodium ascorbic acid.
  • salts of the above-described compounds for example, alkali metal salts, ammonium salts or salts known in the art
  • sodium ascorbic acid such as sodium ascorbic acid.
  • potassium salt of ascorbic acid L-ascorbyl magnesium phosphate may be mentioned.
  • at least one of reductone compound and its oxidant is at least 1 sort (s) selected from (iso) ascorbic acid and its salt, and those oxidants.
  • the salt of (iso) ascorbic acid is preferably an alkali metal salt, more preferably a sodium salt. A mixture of these reductone compounds can be used as necessary.
  • the binder composition is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, particularly preferably at least one of the reductone compound and its oxidant with respect to 100 parts by mass of the particulate polymer. 0.3 parts by mass or more, preferably 5 parts by mass or less, more preferably 2 parts by mass or less, particularly preferably 1 part by mass or less.
  • residual monomers such as (meth) acrylic acid ester monomers having a boiling point of 145 ° C. or more are sufficiently reduced. can do.
  • the content of at least one of the reductone compound and its oxidant is 5 parts by mass or less with respect to 100 parts by mass of the particulate polymer.
  • the amount of gas generated by decomposition of the remaining reductone compound can be reduced by preventing at least one of the compound and its oxidant from remaining in large amounts, and the initial capacity of the secondary battery can be improved. be able to.
  • the binder composition may contain known arbitrary components that can be blended in the binder composition in addition to the components described above. Moreover, residues, such as a polymerization initiator used for superposition
  • the binder composition has a solid content of usually 10% by mass or more, preferably 20% by mass or more, usually 70% by mass or less, preferably 60% by mass or less.
  • content of the (meth) acrylic acid ester monomer with a boiling point of 145 degreeC or more in the binder composition containing the particulate polymer polymerized using the monomer mixture mentioned above is particulate polymer 100 mass. 1500 ⁇ 10 ⁇ 6 parts by mass or less, preferably 1000 ⁇ 10 ⁇ 6 parts by mass or less, more preferably 500 ⁇ 10 ⁇ 6 parts by mass or less, and 300 ⁇ 10 ⁇ 6 parts by mass. It is particularly preferred that the amount is not more than parts.
  • the binder composition has a boiling point of 145 ° C.
  • the (meth) acrylate monomer is often contained in an amount of 1 ⁇ 10 ⁇ 6 parts by mass or more with respect to 100 parts by mass of the particulate polymer.
  • binder is made into the binder composition by making the content rate of the (meth) acrylic acid ester monomer of boiling point 145 degreeC or more in a binder composition into 1500x10-6 mass parts or less with respect to 100 mass parts of particulate polymers.
  • the amount of gas generated in the secondary battery formed using the composition can be reduced, the high-temperature storage characteristics and the high-temperature cycle characteristics can be improved, and the excellent temporal stability of the binder composition can be obtained.
  • a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is polymerized in water until the polymerization conversion becomes 90% by mass or more.
  • Step (1) to obtain a mixture containing a monomer and an unreacted monomer, and after step (1), a reductone compound and a peroxide are added to the mixture to polymerize the unreacted monomer,
  • step (2) of setting the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C.
  • the method for producing the binder composition of the present invention comprises at least two steps: a step of polymerizing the majority of the monomer mixture and a step of further polymerizing the remaining unreacted residual monomer to reduce the amount of residual monomer. And a step of polymerizing the particulate polymer by polymerization.
  • the monomer mixture is preferably emulsified in advance and then added to the reactor for polymerization.
  • step (1) a monomer mixture containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher that can be used for the production of the particulate polymer described above is polymerized in water.
  • the polymerization in the step (1) may be performed in one stage or may be performed in multiple stages.
  • the polymerization conversion rate can be controlled by adjusting the reaction temperature, reaction time, and the like.
  • the polymerization conversion rate in the step (1) is 90% by mass or more, preferably 95% by mass or more is to obtain a particulate polymer having desired properties.
  • the polymerization conversion rate in the step (1) is 90% by mass or more, preferably 95% by mass or more, so that it can be newly generated by redox polymerization in the step (2). It is possible to reduce the amount of the particulate polymer having a property different from that of the particulate polymer.
  • any method such as a suspension polymerization method or an emulsion polymerization method may be used.
  • any of ions, radicals, and living radicals may be used as the reactive species.
  • it is easy to obtain a high molecular weight polymer, and since the polymer is obtained in the form of particles dispersed in water, there is no need for redispersion treatment, and for producing a secondary battery electrode as it is.
  • an emulsion polymerization method is particularly preferable.
  • the emulsion polymerization method can be carried out according to a conventional method (see, for example, “Experimental Chemistry Course” Vol. 28 (Publisher: Maruzen Co., Ltd., edited by The Chemical Society of Japan)).
  • a sealed container equipped with a stirrer and a heating device
  • water an additive such as a dispersant, an emulsifier, a crosslinking agent, a polymerization initiator, and the monomer mixture described above are added so as to have a predetermined composition.
  • a method may be used in which the composition in the container is stirred to emulsify the monomer or the like in water, and the temperature is increased while stirring to initiate polymerization. Or after emulsifying the said composition, it can put into an airtight container, and the method of starting reaction similarly can be used.
  • Examples of the emulsifier used when carrying out the emulsion polymerization in the step (1) include nonionic emulsifiers such as polyoxyethylene alkylene ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester and the like.
  • Anionic emulsifiers such as fatty acids such as myristic acid, palmitic acid, oleic acid, linolenic acid and salts thereof, alkylallyl sulfonates, higher alcohol sulfates, alkyl sulfosuccinic acids; ammonium chlorides such as trimethylammonium chloride and dialkylammonium chloride And cationic emulsifiers such as benzylammonium salts and quaternary ammonium salts; sulfoesters of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carbo Sulphate esters of acids, such as copolymerizable emulsifiers containing a double bond such as sulfoalkyl aryl ether.
  • fatty acids such as myristic acid, palmitic acid, oleic acid, linolenic acid and salts thereof, alkylallyl s
  • emulsifiers can be used alone or in combination of two or more.
  • the amount of the emulsifier used is 0.1 to 10% by mass relative to the monomer mixture. If it is less than 0.1% by mass, aggregates are produced during polymerization. On the other hand, if it exceeds 10% by mass, the average particle size of the obtained particulate polymer becomes small.
  • step (1) water-soluble initiators such as potassium persulfate, ammonium persulfate, and hydrogen peroxide as radical polymerization initiators; benzoyl peroxide, di-t-butyl peroxide, 2,2-azobis-2,4 Oil-soluble initiators such as dimethylvaleronitrile;
  • the addition amount of the polymerization initiator varies depending on each initiator, but in the case of a water-soluble initiator, it is 0.1% by mass or more and 5% by mass or less, and in the case of an oil-soluble initiator, 0.1% by mass or more and 3% by mass % Or less.
  • the reaction temperature in step (1) is usually 0 ° C. or higher, preferably 40 ° C. or higher, usually 150 ° C.
  • the polymerization time is usually 1 hour or more and 20 hours or less. If the polymerization temperature is too low, the reaction rate is too slow and the efficiency is poor, and if the polymerization temperature is too high, the aqueous medium tends to evaporate, making the polymerization difficult.
  • the reaction pressure may be normal pressure. Although the reaction can be carried out in air, it is preferably in the presence of an inert gas such as nitrogen or argon.
  • the dispersant those used in ordinary synthesis may be used.
  • the dispersant include benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate; alkyl sulfates such as sodium lauryl sulfate and sodium tetradodecylsulfate; sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate Sulfosuccinates such as; fatty acid salts such as sodium laurate; ethoxy sulfate salts such as polyoxyethylene lauryl ether sulfate sodium salt, polyoxyethylene nonylphenyl ether sulfate sodium salt; alkane sulfonates; alkyl ether phosphates Sodium salt; polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyoxyethylene- Nonionic
  • benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate; alkyl sulfates such as sodium lauryl sulfate and sodium tetradodecylsulfate can be preferably used. More preferably, benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate can be used from the viewpoint of excellent oxidation resistance. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. The amount of the dispersant is usually 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture.
  • seed polymerization may be performed using seed particles.
  • step (2) Here, in the step (1) described above, it is difficult to set the polymerization conversion rate to 100% by mass, and an unreacted monomer containing a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher remains. To do. Therefore, in the step (2), an unreacted monomer (residual monomer) remaining after the step (1) is polymerized using a redox initiator that uses a reductone compound and a peroxide in combination, and a binder composition is obtained. Reduce the amount of residual monomer in it.
  • step (2) a reductone compound and a peroxide are added to the polymerization system containing a mixture of a polymer and an unreacted monomer obtained through step (1).
  • the redox polymerization is carried out until the content of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher is 1 ⁇ 10 ⁇ 6 parts by mass to 1500 ⁇ 10 ⁇ 6 parts by mass with respect to 100 parts by mass of the polymer.
  • the content ratio of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher should be adjusted by changing the amount of the reductone compound and peroxide used in step (2) and the redox polymerization conditions. Can do.
  • the reaction temperature of the step (2) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, preferably 80 ° C. or lower, more preferably 60 ° C. or lower. If the polymerization temperature is too low, the reaction rate is too slow, so the efficiency is poor, and if the polymerization temperature is too high, the decomposition rate of the redox initiator (reductone compounds and peroxides) is too high, making the polymerization difficult. is there. By performing redox polymerization, the polymerization reaction of the residual monomer can be performed even under such a mild temperature condition.
  • the polymerization time in step (2) is preferably 1 hour or more and 6 hours or less.
  • the temperature of the polymerization system is set to a temperature higher than the polymerization temperature at the time of redox polymerization (for example, more than 80 ° C ), It is preferable to remove or decompose the peroxide.
  • the pressure of the reaction in the step (2) may be a normal pressure.
  • the reaction can be carried out in air, it is preferably in the presence of an inert gas such as nitrogen or argon.
  • the amount of the reductone compound is appropriately changed according to the kind of the peroxide, but is preferably 0.05% by mass or more, preferably with respect to the amount of the monomer mixture used in the step (1). 0.1 mass% or more, usually 5 mass% or less, preferably 1 mass% or less.
  • the amount of the reductone compound used is too small, redox polymerization does not proceed sufficiently, and the residual monomer reducing effect may be insufficient.
  • the reductone compounds may be added all at once or dividedly, but in terms of improving the residual monomer reduction efficiency, divided addition is preferred.
  • the blending amount of the polymerization initiator is reduced as compared with the case where other polymerization methods are employed to reduce the residual monomer, and polymerization is started in the binder composition. It is possible to prevent the residue of the agent from remaining in large quantities.
  • the reductone compounds used in the step (2) can include the reductone compounds exemplified in the section of the binder composition, and as mentioned above, ascorbic acid, its isomers and derivatives, and salts thereof. Is preferred.
  • the peroxide include water-soluble peroxides exemplified below. Since the binder composition of this invention is a binder composition used for manufacture of a secondary battery, it is preferable to use the peroxide which does not contain a transition metal element. In addition, that the peroxide is “water-soluble” means that it has a water solubility of 5% by mass or more in water at 25 ° C.
  • peroxide that can be used in the present invention, hydrogen peroxide, peroxy acid salt, peroxodisulfuric acid and its salt, peroxy ester salt, peroxide ammonium or alkali metal salt, perborate, persulfate And tert-butyl hydroperoxide (t-BuOOH), benzoyl peroxide.
  • tert-butyl hydroperoxide, hydrogen peroxide, and peracetic acid are preferable, and tert-butyl hydroperoxide is particularly preferable. This is because radical species generated from peroxides that are water-soluble and have a low molecular weight have high molecular mobility and can reduce residual monomers effectively because of their low molecular weight.
  • the amount of peroxide used is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 5% by mass or less, based on the amount of the monomer mixture used in step (1). More preferably, it is 1 mass% or less.
  • the slurry composition for secondary battery electrodes of the present invention is characterized by containing the above-mentioned binder composition and electrode active material (positive electrode active material or negative electrode active material).
  • electrode active material positive electrode active material or negative electrode active material.
  • the slurry composition for secondary battery electrodes of the present invention may contain a conductive material, a viscosity modifier, a surfactant, a dispersant and the like in addition to the binder composition and the electrode active material.
  • the ratio of the binder composition contained in the slurry composition of the present invention can be adjusted as appropriate so that the performance of the obtained battery is satisfactorily exhibited.
  • the ratio of the solid content of the binder composition to 100 parts by mass of the electrode active material is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, and usually 50 parts by mass.
  • Part or less preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 3 parts by weight or less.
  • a negative electrode active material When using a slurry composition for formation of a negative electrode, a negative electrode active material is used as an electrode active material.
  • the negative electrode active material is an electrode active material used in the negative electrode, and is a material that transfers electrons in the negative electrode of the secondary battery.
  • a material that can occlude and release lithium is usually used as the negative electrode active material. Examples of the material that can occlude and release lithium include a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material obtained by combining these materials.
  • the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton into which lithium can be inserted (also referred to as “dope”).
  • Examples of the carbon-based negative electrode active material include a carbonaceous material and a graphite material. Is mentioned.
  • the carbonaceous material is a material having a low degree of graphitization (ie, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or lower.
  • the minimum of the heat processing temperature at the time of carbonizing is not specifically limited, For example, it can be 500 degreeC or more.
  • Examples of the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
  • the graphitizable carbon for example, a carbon material using tar pitch obtained from petroleum or coal as a raw material can be mentioned. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fibers, pyrolytic vapor grown carbon fibers, and the like.
  • examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.
  • the graphite material is a material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher.
  • the upper limit of heat processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
  • the graphite material include natural graphite and artificial graphite.
  • the artificial graphite for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. Examples thereof include graphitized mesophase pitch-based carbon fibers that have been heat-treated.
  • the metal-based negative electrode active material is an active material containing a metal, and usually contains an element capable of inserting lithium in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh / g or more.
  • the metal active material include lithium metal and a single metal capable of forming a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn). , Sr, Zn, Ti, etc.) and alloys thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof.
  • active materials containing silicon are preferable. This is because the capacity of the lithium ion secondary battery can be increased by using the silicon-based negative electrode active material.
  • silicon-based negative electrode active materials examples include silicon (Si), alloys of silicon and cobalt, nickel, iron, etc., SiO, SiOx, mixtures of Si-containing materials and carbon materials, and Si-containing materials coated with conductive carbon.
  • Si silicon
  • alloys of silicon and cobalt nickel, iron, etc.
  • SiO, SiOx mixtures of Si-containing materials and carbon materials
  • Si-containing materials coated with conductive carbon examples include silicon (Si), alloys of silicon and cobalt, nickel, iron, etc., SiO, SiOx, mixtures of Si-containing materials and carbon materials, and Si-containing materials coated with conductive carbon.
  • Si-containing materials coated with conductive carbon.
  • a composite of a Si-containing material and conductive carbon formed into a composite can be used.
  • SiOx is a compound containing at least one of SiO and SiO 2 and Si, and x is usually 0.01 or more and less than 2.
  • SiOx can be formed using the disproportionation reaction of a silicon monoxide (SiO), for example.
  • SiOx can be prepared by heat-treating SiO, optionally in the presence of a polymer such as polyvinyl alcohol, to produce silicon and silicon dioxide. The heat treatment can be performed at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher, in an atmosphere containing an organic gas and / or steam after grinding and mixing SiO and optionally a polymer.
  • Si-containing material such as silicon and SiOx
  • carbon material such as carbonaceous material and graphite material
  • a polymer such as polyvinyl alcohol. Things.
  • carbonaceous material and a graphite material the material which can be used as a carbon-type negative electrode active material can be used.
  • a composite of Si-containing material and conductive carbon for example, a pulverized mixture of SiO, a polymer such as polyvinyl alcohol, and optionally a carbon material is heat-treated in an atmosphere containing, for example, an organic gas and / or steam.
  • a known method such as a method of coating the surface of SiO particles with an organic gas or the like by chemical vapor deposition, or a composite particle (granulation) of SiO particles and graphite or artificial graphite by a mechanochemical method. Can be used.
  • the negative electrode active material when a carbon-based negative electrode active material or a metal-based negative electrode active material is used as the negative electrode active material, these negative electrode active materials expand and contract as the lithium ion secondary battery is charged and discharged. Therefore, when these negative electrode active materials are used, normally, the negative electrode gradually expands due to repeated expansion and contraction of the negative electrode active material, the secondary battery is deformed, and electrical characteristics such as cycle characteristics are obtained. May be reduced.
  • the negative electrode bulge caused by expansion and contraction of the negative electrode active material is suppressed by the cross-linked structure formed due to the cross-linkable monomer described above. Electrical characteristics such as cycle characteristics can be improved.
  • capacitance of a lithium ion secondary battery can be increased if the said silicon-type negative electrode active material is used, generally a silicon-type negative electrode active material expand
  • the negative electrode active material when a mixture of a carbon-based negative electrode active material and a silicon-based negative electrode active material is used as the negative electrode active material, from the viewpoint of sufficiently increasing the capacity of the lithium ion secondary battery while sufficiently suppressing the occurrence of swelling of the negative electrode. It is preferable to use artificial graphite as the carbon-based negative electrode active material, and as the silicon-based negative electrode active material, Si, SiOx, a mixture of a Si-containing material and a carbon material, and a composite of a Si-containing material and conductive carbon.
  • a composite of a Si-containing material and conductive carbon as the silicon-based negative electrode active material, and a composite in which SiOx is dispersed in a conductive carbon matrix. It is particularly preferable to use (Si—SiOx—C composite). While these negative electrode active materials can occlude and release a relatively large amount of lithium, the volume change when lithium is occluded and released is relatively small. Therefore, if these negative electrode active materials are used, a lithium ion secondary using a negative electrode for a lithium ion secondary battery formed using the slurry composition while suppressing an increase in volume change of the negative electrode active material during charge / discharge. The capacity of the battery can be sufficiently increased.
  • the particle size and specific surface area of the negative electrode active material are not particularly limited, and can be the same as those of conventionally used negative electrode active materials.
  • the content ratio of the negative electrode active material in the slurry composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, preferably 99.9% by mass or less, more preferably 99% by mass or less. .
  • the capacity of the secondary battery of the present invention can be increased, and the flexibility of the negative electrode and the binding property between the current collector and the negative electrode mixture layer are improved. Can be made.
  • a positive electrode active material is used as the electrode active material.
  • the positive electrode active material is an electrode active material used in the positive electrode, and is a material that transfers electrons in the positive electrode of the secondary battery.
  • the secondary battery of the present invention is a lithium ion secondary battery
  • a material capable of inserting and extracting lithium ions is usually used as the positive electrode active material.
  • Such positive electrode active materials are roughly classified into those made of inorganic compounds and those made of organic compounds.
  • Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
  • Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
  • Examples of the transition metal oxide include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13 and the like are mentioned, and among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity of the secondary battery.
  • transition metal sulfide examples include TiS 2 , TiS 3 , amorphous MoS 2 , and FeS.
  • lithium-containing composite metal oxide examples include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, Ni—Mn— Examples thereof include a lithium composite oxide of Al, a lithium composite oxide of Ni—Co—Al, and a solid solution of LiMaO 2 and Li 2 MbO 3 . Examples of the solid solution of LiMaO 2 and Li 2 MbO 3 include xLiMaO 2. (1-x) Li 2 MbO 3 .
  • x represents a number satisfying 0 ⁇ x ⁇ 1
  • Ma represents one or more transition metals having an average oxidation state of 3+
  • Mb represents one or more transition metals having an average oxidation state of 4+.
  • LiCoO 2 is preferably used from the viewpoint of improving the cycle characteristics of the secondary battery
  • LiMaO is used from the viewpoint of improving the energy density of the secondary battery.
  • a solid solution of 2 and Li 2 MbO 3 is preferred.
  • xLiMaO 2 ⁇ (1-x) Li 2 MbO 3 (x represents a number satisfying 0 ⁇ x ⁇ 1, Ma is Ni, Co, Mn Mb represents one or more selected from the group consisting of Mn, Zr and Ti).
  • xLiMaO 2 ⁇ (1-x) Li 2 MnO 3 (x represents a number satisfying 0 ⁇ x ⁇ 1, and Ma is one or more selected from the group consisting of Ni, Co, Mn, Fe, and Ti. Is preferred).
  • An example of such a solid solution is Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 .
  • Examples of the lithium-containing composite metal oxide having a spinel structure include compounds in which a part of Mn of lithium manganate (LiMn 2 O 4 ) is substituted with another transition metal.
  • LiMn 2 O 4 lithium manganate
  • a specific example is Li s [Mn 2 ⁇ t Md t ] O 4 .
  • Md represents one or more transition metals having an average oxidation state of 4+.
  • Specific examples of Md include Ni, Co, Fe, Cu, and Cr.
  • T represents a number satisfying 0 ⁇ t ⁇ 1, and s represents a number satisfying 0 ⁇ s ⁇ 1.
  • a lithium-excess spinel compound represented by Li 1 + x Mn 2 ⁇ x O 4 (0 ⁇ X ⁇ 2) can also be used.
  • s represents a number satisfying 0 ⁇ s ⁇ 1
  • t represents a number satisfying 0 ⁇ t ⁇ 1
  • z represents a number satisfying 0 ⁇ z ⁇ 0.1.
  • LiNi 0.5 Mn 1.5 O 4 in which Mn of lithium manganate is substituted with Ni is also preferable.
  • LiNi 0.5 Mn 1.5 O 4 and the like can replace all of Mn 3+ considered to be a factor of structural deterioration.
  • LiNi 0.5 Mn 1.5 O 4 and the like undergo an electrochemical reaction from Ni 2+ to Ni 4+ , a secondary battery having a high operating voltage and a high capacity can be realized.
  • Examples of the lithium-containing composite metal oxide having an olivine type structure include an olivine type lithium phosphate compound represented by Li y McPO 4 .
  • Mc represents one or more transition metals having an average oxidation state of 3+, and examples thereof include Mn, Fe, and Co.
  • Y represents a number satisfying 0 ⁇ y ⁇ 2.
  • Mn or Co may be partially substituted with another metal.
  • the metal that can be substituted include Fe, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B, and Mo.
  • examples of the positive electrode active material made of an inorganic compound include a positive electrode active material having a polyanion structure such as Li 2 MeSiO 4 , LiFeF 3 having a perovskite structure, and Li 2 Cu 2 O 4 having an orthorhombic structure. Can be mentioned.
  • Me represents Fe or Mn.
  • examples of the positive electrode active material made of an organic compound include conductive polymers such as polyacetylene and poly-p-phenylene.
  • a composite material covered with a carbon material may be produced by reducing and firing an iron-based oxide in the presence of a carbon source material, and this composite material may be used as a positive electrode active material.
  • Iron-based oxides tend to have poor electrical conductivity, but can be used as a high-performance positive electrode active material by using a composite material as described above.
  • the positive electrode active material is preferably a lithium-containing composite metal oxide because it has a high energy density.
  • Many lithium-containing composite metal oxides have a hydrophilic group as a surface functional group. Therefore, by using the lithium-containing composite metal oxide, a slurry composition having high dispersion stability can be obtained, and the binding between the positive electrode active materials in the electrode can be kept strong.
  • the surface state of the positive electrode active material can be determined by measuring the contact angle between the positive electrode active material and the solvent. For example, it can be confirmed by pressure-molding only the positive electrode active material to produce pellets and determining the contact angle of the pellets with a polar solvent (for example, N-methylpyrrolidone). A lower contact angle indicates that the positive electrode active material is more hydrophilic.
  • examples of the positive electrode active material include nickel hydroxide particles.
  • the nickel hydroxide particles may be dissolved in cobalt, zinc, cadmium, or the like, or may be coated with a cobalt compound whose surface is subjected to an alkali heat treatment.
  • the positive electrode active material may be partially element-substituted.
  • an inorganic compound and an organic compound may be used in combination.
  • one type of positive electrode active material may be used alone, or two or more types may be used in combination at any ratio.
  • the particle size of the positive electrode active material particles is usually selected as appropriate in consideration of other constituent requirements of the secondary battery.
  • the 50% volume cumulative diameter of the positive electrode active material particles is usually 0.1 ⁇ m or more, preferably 0.4 ⁇ m or more, more preferably 1 ⁇ m or more, from the viewpoint of improving battery characteristics such as load characteristics and cycle characteristics. It is 50 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less. When the 50% volume cumulative diameter is within this range, a secondary battery having excellent output characteristics and a large charge / discharge capacity can be obtained. Moreover, the handling at the time of manufacturing the slurry composition for manufacturing a positive electrode compound material layer and manufacturing a positive electrode is easy.
  • the 50% volume cumulative diameter can be determined by measuring the particle size distribution by laser diffraction.
  • lithium-containing nickel oxide (LiNiO 2 ), lithium-containing cobalt oxide (LiCoO). 2 ), Co—Ni—Mn lithium composite oxide (Li (Co 2 Mn Ni) O 2 ), Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 , LiNi 0.5 Mn 1.5 O 4 and the like are preferable.
  • Co-Ni-Mn lithium composite oxide (Li (Co Mn Ni) O 2 ) and lithium-containing cobalt oxide (LiCoO 2 ) are preferable.
  • the content ratio of the positive electrode active material in the slurry composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less. is there. By setting the content ratio of the positive electrode active material in the slurry composition within the above range, a good slurry composition and positive electrode can be produced.
  • the said slurry composition contains a electrically conductive material.
  • the conductive material include particles made of carbon allotrope having conductivity.
  • the conductive material include conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor grown carbon fiber, and carbon nanotube. Further, for example, carbon powder such as graphite, fibers and foils of various metals, and the like are also included.
  • a conductive material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • acetylene black is used as the conductive material from the viewpoint of improving the electrical contact between the positive electrode active materials and improving the electrical characteristics of the secondary battery using the positive electrode formed using the slurry composition. It is preferable.
  • the 50% volume cumulative diameter of the conductive material is preferably smaller than the 50% volume cumulative diameter of the positive electrode active material.
  • the specific range of the 50% volume cumulative diameter of the conductive material is usually 0.001 ⁇ m or more, preferably 0.05 ⁇ m or more, more preferably 0.01 ⁇ m or more, and usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 1 ⁇ m. It is as follows. When the 50% volume cumulative diameter of the conductive material is within this range, high conductivity can be obtained with a smaller amount of use.
  • the amount of the conductive material is usually 0.01 parts by mass or more, preferably 1 part by mass or more, and usually 20 parts by mass or less, preferably 10 parts by mass or less with respect to 100 parts by mass of the positive electrode active material.
  • the amount of the conductive material When the amount of the conductive material is within this range, the capacity of the secondary battery can be increased and high load characteristics can be exhibited. If the amount of the conductive material is too small, the conductive path formed by electrical contact between the positive electrode active materials becomes insufficient, and the output of the secondary battery may be reduced. On the other hand, when the blending amount of the conductive material is too large, the stability of the slurry composition is lowered and the density of the positive electrode mixture layer in the positive electrode is lowered, so that the capacity of the lithium ion secondary battery cannot be sufficiently increased. .
  • the viscosity modifier is for adjusting the viscosity of the slurry composition and facilitating the application of the slurry composition on the current collector.
  • a water-soluble polymer can be used as the viscosity modifier.
  • examples of the viscosity modifier include cellulose polymers such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, and ammonium salts and alkali metal salts of these cellulose polymers; modified or unmodified poly (meth) acrylic Acids and ammonium and alkali metal salts of these poly (meth) acrylic acids; modified or unmodified polyvinyl alcohol, copolymers of acrylic acid or acrylates with vinyl alcohol, maleic anhydride, maleic acid or Polyvinyl alcohols such as copolymers of fumaric acid and vinyl alcohol; polyethylene glycol, polyvinyl pyrrolidone, modified polyacrylic acid, oxidized starch, phosphate starch, casein, various modified starches, acrylonitrile Butadiene copolymer hydrides can be used.
  • any polymer that is water-soluble and has a thiol group at the terminal water-soluble polymer having a thiol group at the terminal
  • the compounding quantity of a viscosity modifier is 0.1 mass part or more normally per 100 mass parts of electrode active materials, Preferably, it is 0.3 mass part or more, Usually 2 mass parts or less, Preferably it is 1 mass part or less.
  • the blending amount of the viscosity modifier is within the above range, a slurry composition having a good viscosity can be obtained. Therefore, the slurry composition can be satisfactorily applied onto the current collector during electrode formation, and as a result, the product life of the obtained electrode can be extended.
  • the slurry composition of the present invention may further contain a surfactant.
  • the surfactant is effective for preventing the repelling that occurs when applying the slurry composition to the current collector and improving the smoothness of the electrode.
  • examples of the surfactant include alkyl surfactants, silicon surfactants, fluorine surfactants, metal surfactants, and the like.
  • the compounding amount of the surfactant is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the electrode active material. When the surfactant is in the above range, productivity and smoothness during electrode production are improved, and the battery characteristics of the secondary battery are excellent.
  • the slurry composition of the present invention may further contain a dispersant.
  • the dispersant include an anionic compound, a cationic compound, a nonionic compound, and a polymer compound.
  • a specific dispersing agent is selected according to the electrode active material and conductive material to be used. By using the dispersant, the stability of the slurry composition is improved and a smooth electrode is obtained, so that the battery capacity of the secondary battery can be increased.
  • the amount of the dispersing agent is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, and usually 10 parts by mass with respect to 100 parts by mass of the electrode active material. Part or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less.
  • the slurry composition of the present invention may contain components such as a reinforcing material, an antioxidant, and an electrolytic solution additive having a function of suppressing decomposition of the electrolytic solution.
  • components such as a reinforcing material, an antioxidant, and an electrolytic solution additive having a function of suppressing decomposition of the electrolytic solution.
  • known ones can be used. For example, those described in International Publication No. 2012/115096, International Publication No. 2012/036260, and Japanese Patent Application Laid-Open No. 2012-204303 can be used. it can.
  • the slurry composition of the present invention can be prepared by dispersing each of the above components in an aqueous medium as a dispersion medium. Specifically, the above components and the aqueous medium are mixed using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix. Thus, a slurry composition can be prepared.
  • a slurry composition can be prepared.
  • water is usually used, but an aqueous solution of an arbitrary compound or a mixed solution of a small amount of an organic medium and water may be used.
  • the solid content concentration of the slurry composition can be set to a concentration at which each component can be uniformly dispersed, for example, 10 to 80% by mass. Further, the mixing of each of the above components and the aqueous medium can be usually carried out in the range of room temperature to 80 ° C. for 10 minutes to several hours.
  • the viscosity of the slurry composition is preferably 10 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more, preferably 100,000 mPa ⁇ s or less, more preferably from the viewpoint of the temporal stability and coating properties of the slurry composition. Is 50,000 mPa ⁇ s or less.
  • the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
  • the pH of the said slurry composition is 7 or more normally, Preferably it is 8 or more, Usually, 12 or less, Preferably it is 11.5 or less.
  • a method of adjusting the pH of the slurry composition for example, a method of adjusting the pH of the slurry composition by washing the positive electrode active material before preparing the slurry composition, bubbling carbon dioxide gas to the prepared slurry composition Examples thereof include a method for adjusting pH and a method for adjusting using a pH adjusting agent.
  • a pH adjuster is a water-soluble substance which shows acidity. Either a strong acid or a weak acid may be used.
  • water-soluble substances that exhibit weak acidity include organic compounds having an acid group such as a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.
  • an organic compound having a carboxylic acid group is particularly preferably used.
  • Specific examples of the compound having a carboxylic acid group include succinic acid, phthalic acid, maleic acid, succinic anhydride, phthalic anhydride, maleic anhydride and the like. These compounds can be made into acid anhydrides having little influence in the secondary battery by drying.
  • water-soluble substances that exhibit strong acidity include hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.
  • pH adjusting agents described above it is preferable that they are decomposed or volatilized in the drying step of the slurry composition. In this case, no pH adjuster remains in the obtained positive electrode.
  • examples of such a pH adjuster include acetic acid and hydrochloric acid.
  • a pH adjuster may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the pH of the slurry composition may be adjusted at any time as long as it is during the production process of the slurry composition. Especially, after adjusting a slurry composition to desired solid content concentration, it is preferable to adjust pH with a pH adjuster. By adjusting the pH after adjusting the slurry composition to a predetermined solid content concentration, it is possible to easily adjust the pH while preventing dissolution of the positive electrode active material.
  • the slurry composition of the present invention is prepared by preparing the binder composition of the present invention and then mixing the binder composition and the electrode active material, or dispersing them in an aqueous medium as a dispersion medium. Also good.
  • the secondary battery electrode of the present invention is obtained by applying the slurry composition for a secondary battery electrode obtained as described above on a current collector, and applying the slurry for the secondary battery electrode on the current collector. It is obtained by drying the composition.
  • the electrode for a secondary battery of the present invention includes a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer includes at least an electrode active material and a particulate weight. The merger is included.
  • each component such as an electrode active material contained in the electrode mixture layer is contained in the slurry composition of the present invention, and a suitable abundance ratio of these components is determined according to the present invention. It is the same as the preferred abundance ratio of each component in the slurry composition.
  • a method for applying the slurry composition for a secondary battery electrode on the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the slurry composition may be applied to only one side of the current collector or may be applied to both sides. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the electrode mixture layer obtained by drying.
  • the current collector to which the slurry composition is applied is not particularly limited as long as it is a material having electrical conductivity and electrochemical durability.
  • the current collector is preferably made of metal, such as iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, or platinum.
  • a copper foil is particularly preferable as the current collector used for the negative electrode
  • aluminum is particularly preferable as the current collector used for the positive electrode.
  • One type of current collector material may be used alone, or two or more types may be used in combination at any ratio.
  • the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 mm to 0.5 mm is preferable.
  • the current collector is used after roughening the surface in advance in order to increase the adhesive strength of the electrode mixture layer.
  • the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • a mechanical polishing method usually, a polishing cloth with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
  • a method for drying the slurry composition on the current collector is not particularly limited, and a known method can be used. For example, drying with warm air, hot air, low-humidity air, vacuum drying, irradiation with infrared rays, electron beams, or the like. A drying method is mentioned. Thus, by drying the slurry composition on the current collector, an electrode mixture layer is formed on the current collector, and a lithium ion secondary battery electrode including the current collector and the electrode mixture layer is obtained. be able to.
  • the electrode mixture layer may be subjected to pressure treatment using a die press or a roll press.
  • the pressure treatment can improve the adhesion between the electrode mixture layer and the current collector and reduce the porosity of the electrode.
  • the porosity is preferably 5% or more, more preferably 7% or more, preferably 15% or less, more preferably 13% or less.
  • the thickness of the electrode mixture layer is usually 5 ⁇ m or more, preferably 10 ⁇ m or more, and usually 300 ⁇ m or less, preferably 250 ⁇ m or less. When the thickness of the electrode mixture layer is in the above range, both load characteristics and energy density are high.
  • the water content in the electrode mixture layer is preferably 1000 ppm or less, and more preferably 500 ppm or less. By setting the water content of the electrode mixture layer within the above range, a secondary battery electrode having excellent durability can be realized. The amount of water can be measured by a known method such as the Karl Fischer method.
  • the powder molding method refers to preparing a slurry composition for producing an electrode for a secondary battery, preparing composite particles including an electrode active material from the slurry composition, and placing the composite particles on a current collector. It is a manufacturing method which supplies the electrode for secondary batteries by forming an electrode compound-material layer by supplying and roll-pressing as needed and shaping
  • the secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and uses the secondary battery electrode of the present invention as at least one of the positive electrode and the negative electrode.
  • the secondary battery of the present invention is excellent in high temperature storage characteristics and high temperature cycle characteristics, and gas generation is suppressed.
  • the secondary battery of the present invention may be any of a lithium ion secondary battery, a nickel hydride secondary battery, and the like. Among these, lithium ion secondary batteries are preferable because performance improvement effects such as improvement of cycle characteristics and output characteristics are particularly remarkable.
  • the secondary battery of the present invention is a lithium ion secondary battery will be described.
  • At least one of the positive electrode and the negative electrode may be the electrode for the secondary battery of the present invention. That is, a known electrode may be used as either the positive electrode or the negative electrode.
  • Examples of known positive electrodes include those usually comprising a current collector and a positive electrode mixture layer formed on the surface of the current collector.
  • the positive electrode mixture layer comprises a positive electrode active material, a conductive material and a binder.
  • the positive electrode active material, and the conductive material those described above in the sections of “secondary battery electrode” and “secondary battery electrode slurry composition” can be used.
  • the binder any known binder can be used as long as the present invention is not significantly impaired.
  • the positive electrode mixture layer may contain components other than the positive electrode active material, the conductive material, and the binder as necessary, for example, the components listed as “other components” in the section of “Slurry composition for secondary battery electrode”. It may be included. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the negative electrode there is usually one having a current collector and a negative electrode mixture layer formed on the surface of the current collector, and the negative electrode mixture layer contains a negative electrode active material and a binder.
  • the current collector and the negative electrode active material those described above in the sections of “secondary battery electrode” and “secondary battery electrode slurry composition” can be used.
  • the binder any known binder can be used as long as the present invention is not significantly impaired. Examples of such binders include polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, and polyacrylonitrile derivatives.
  • a soft polymer such as an acrylic soft polymer, a diene soft polymer, an olefin soft polymer, or a vinyl soft polymer may be used. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the negative electrode mixture layer contains components other than the negative electrode active material and the binder, for example, the components listed as “other components” in the section of “slurry composition for secondary battery electrode” as necessary. May be. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the total thickness of these electrodes is usually 5 ⁇ m or more, preferably 10 ⁇ m or more, and usually 300 ⁇ m or less, preferably 250 ⁇ m or less. When the thickness of the electrode is in the above range, both load characteristics and energy density can be improved.
  • Electrodes prepare the slurry composition for electrodes containing an electrode active material, a binder, and water similarly to the electrode for secondary batteries of this invention, for example,
  • the layer of the slurry composition is used as a collector. It may be formed and the layer dried.
  • Electrode As an electrolytic solution for a lithium ion secondary battery, for example, a nonaqueous electrolytic solution in which a supporting electrolyte is dissolved in a nonaqueous solvent is used.
  • a lithium salt is usually used.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the concentration of the supporting electrolyte in the electrolytic solution is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less. Depending on the type of supporting electrolyte, it may be used usually at a concentration of 0.5 mol / L to 2.5 mol / L. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity may decrease.
  • the non-aqueous solvent is not particularly limited as long as it can dissolve the supporting electrolyte.
  • non-aqueous solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC); and esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide; Among these, carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
  • a non-aqueous solvent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • an additive in electrolyte solution examples include carbonate compounds such as vinylene carbonate (VC).
  • An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • an electrolytic solution other than the above for example, a polymer electrolyte such as polyethylene oxide or polyacrylonitrile; a gel polymer electrolyte obtained by impregnating the polymer electrolyte with an electrolytic solution; an inorganic solid electrolyte such as LiI or Li 3 N; Also good.
  • a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing an aromatic polyamide resin; a porous resin coat containing an inorganic ceramic powder;
  • microporous membranes made of polyolefin resins (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as mixtures or copolymers thereof; polyethylene terephthalate, polycycloolefin, polyether sulfone, polyamide, Examples thereof include a microporous film made of a resin such as polyimide, polyimide amide, polyaramid, polycycloolefin, nylon, and polytetrafluoroethylene; a polyolefin fiber woven or non-woven fabric thereof; an aggregate of insulating substance particles, and the like.
  • a microporous film made of a polyolefin-based resin is preferable
  • the thickness of the separator is usually 0.5 ⁇ m or more, preferably 1 ⁇ m or more, and usually 40 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less. Within this range, the resistance due to the separator in the secondary battery is reduced, and the workability when manufacturing the secondary battery is excellent.
  • a positive electrode and a negative electrode are overlapped via a separator, and this is wound into a battery container according to the shape of the battery.
  • the method of injecting and sealing is mentioned.
  • an expanded metal; an overcurrent prevention element such as a fuse or a PTC element; a lead plate or the like may be inserted to prevent an increase in pressure inside the battery or overcharge / discharge.
  • the shape of the secondary battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
  • the manufactured laminated cell type lithium ion secondary battery was charged to 4.3 V by a constant current method of 0.1 C in a 25 ° C. environment, and then stored at 80 ° C. for 50 hours.
  • the cell of the laminated cell type lithium ion secondary battery was sandwiched between glass plates, and the thickness of the cell was measured with a micro gauge.
  • the thickness of the cell before storage at 80 ° C. is a
  • the thickness of the cell after storage at 80 ° C. for 50 hours is b
  • the thickness ratio (b / a) before and after storage at 80 ° C. is determined. did. It shows that the smaller the calculated ratio (b / a), the smaller the gas generation amount and the better the gas generation suppression effect.
  • Ratio (b / a) is 1.00 times or more and 1.05 times or less
  • B: Ratio (b / a) is more than 1.05 times and 1.10 times or less
  • D: Ratio (b / a) is more than 1.15 times and less than 1.20 times
  • the manufactured laminated cell type lithium ion secondary battery was charged to 4.3 V by a constant current method of 0.1 C in a 25 ° C. environment, and then stored at 80 ° C. for 100 hours.
  • the open circuit voltage (Open circuit voltage, hereinafter referred to as “OCV”) before the start of storage at 80 ° C. and the OCV of the cell after storage for 100 hours at 80 ° C. were measured.
  • the OCV ratio after storage for 100 hours is defined as the OCV maintenance rate, and is determined according to the following criteria. It shows that it is excellent in a high temperature storage characteristic, ie, a lifetime characteristic, so that an OCV maintenance factor is large.
  • OCV maintenance rate is 99.0% or more
  • B OCV maintenance rate is 98.8% or more and less than 99.0%
  • C OCV maintenance rate is 98.6% or more and less than 98.8%
  • D OCV maintenance rate is 98 0.4% or more and less than 98.6%
  • E OCV maintenance rate is 98.2% or more and less than 98.4%
  • F OCV maintenance rate is 98.0% or more and less than 98.2%
  • Capacity maintenance rate is 90% or more
  • ⁇ Peel strength (adhesiveness between negative electrode mixture layer and current collector)>
  • the produced negative electrode for a secondary battery was cut into a rectangular shape having a length of 100 mm and a width of 10 mm to obtain a test piece.
  • a stress was measured when one end of the current collector was pulled in a vertical direction at a pulling speed of 50 mm / min and peeled off (the cellophane tape was fixed to the test stand). The measurement was performed three times, the average value was obtained and this was taken as the peel peel strength, and evaluated according to the following criteria. It shows that it is excellent in the adhesiveness of a negative mix layer and a collector, so that the value of peeling peel strength is large.
  • Peel peel strength is 30 N / m or more
  • B Peel peel strength is 25 N / m or more and less than 30 N / m
  • C Peel peel strength is 20 N / m or more and less than 25 N / m
  • D Peel peel strength is less than 20 N / m
  • the amount of (meth) acrylic acid ester monomer (residual monomer) in the binder composition was measured by gas chromatography. Specifically, first, a sample for measurement was prepared by diluting with acetone so that the solid content concentration of the particulate polymer in the binder composition was 1% by mass and filtering using 5C filter paper. And about the prepared sample, the gas chromatography was implemented on condition of the following.
  • Apparatus Agilent 6850A (manufactured by Agilent Technologies) Column: HP-1 Average linear velocity: 15 cm / s Injection volume: 1ml Inlet temperature: 250 ° C Split ratio: 20: 1 Detector: Flame ionization detector (FID) Detector temperature: 280 ° C Oven: Hold at 40 ° C for 3 minutes, then heat at 10 ° C / minute and hold at 280 ° C for 5 minutes
  • volume average particle size of the particulate polymer was measured using a light scattering particle size measuring device (Coulter LS230, manufactured by Coulter Inc.).
  • the binder composition for secondary battery electrodes of the present invention was used for forming a negative electrode, the case where it was used for forming a positive electrode was evaluated.
  • the binder composition of the present invention was used for forming a negative electrode.
  • styrene as an aromatic vinyl monomer
  • acidic An emulsion was prepared by adding 8.0 parts of itaconic acid (IA) as a group-containing monomer and 4.8 parts of sodium lauryl sulfate and 192 parts of ion-exchanged water as a dispersant. This emulsion was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes. Thereafter, the mixture was stirred for about 120 minutes, and when the polymerization conversion rate (monomer consumption amount) reached 93%, it was cooled to 40 ° C.
  • IA itaconic acid
  • the obtained particulate polymer had a glass transition temperature of ⁇ 6.2 ° C. and a volume average particle size of 0.167 ⁇ m.
  • the content of the (meth) acrylic acid ester monomer unit having a boiling point of 145 ° C. or higher in the particulate polymer is 50%, the content of the acidic group-containing monomer unit is 2%, and the aromatic vinyl monomer unit. was 47%, and the crosslinkable monomer unit content was 1%.
  • the content of the (meth) acrylic acid ester monomer (2-EHA) having a boiling point of 145 ° C. or higher with respect to 100 parts by mass of the particulate polymer was 208 ⁇ 10 ⁇ 6 parts by mass.
  • This negative electrode slurry composition was applied to one side of a 10 ⁇ m thick copper foil, dried at 110 ° C. for 3 hours, and then roll pressed to obtain a negative electrode having a negative electrode mixture layer having a thickness of 60 ⁇ m. About the obtained negative electrode, peel strength was measured. The results are shown in Table 1.
  • Co-Ni-Mn lithium composite oxide based active material product name: Cellseed NMC613, manufactured by Nippon Chemical Industry Co., Ltd .; hereinafter sometimes referred to as “NMC”
  • NMC Cellseed NMC613, manufactured by Nippon Chemical Industry Co., Ltd .
  • CMC sodium salt
  • BM-610B binder solid content concentration 40%
  • the obtained positive electrode slurry composition was applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 3 hours, and then roll-pressed to obtain a positive electrode having a positive electrode mixture layer having a thickness of 50 ⁇ m.
  • a battery container was prepared using a laminate film made of an aluminum sheet and a polypropylene resin covering both surfaces thereof. Subsequently, the mixture layer was removed from the end portions of the positive electrode and the negative electrode obtained above to form a portion where the copper foil or the aluminum foil was exposed. A Ni tab was welded to the portion where the aluminum foil of the positive electrode was exposed, and a Cu tab was welded to the portion where the copper foil of the negative electrode was exposed. The obtained tabbed positive electrode and tabbed negative electrode were stacked with a separator made of a polyethylene microporous film interposed therebetween.
  • the direction of the surface of the electrode was such that the surface on the positive electrode mixture layer side and the surface of the negative electrode mixture layer side face each other.
  • the stacked electrode and separator were wound and stored in the battery container.
  • the electrolytic solution a solution prepared by dissolving LiPF 6 to a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 2 at 25 ° C. was used. .
  • the laminate film was sealed to produce a laminate cell type lithium ion secondary battery which is the lithium ion secondary battery of the present invention.
  • the amount of gas generation, high temperature storage characteristics, and high temperature cycle characteristics of the obtained laminated cell type lithium ion secondary battery were evaluated. The results are shown in Table 1.
  • Example 2 Table 1 shows the blending amount of 2-ethylhexyl acrylate, which is a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher, blending amount of styrene, which is an aromatic vinyl monomer, and the polymerization conversion rate in step (1).
  • a binder composition was prepared in the same manner as in Example 1 except that the composition was changed as shown in FIG. In addition, even if it was a case where the compounding quantity of each component was changed, the ratio between the compounding quantities of each component contained in superposition
  • the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition.
  • the peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 3 Example 1 except that the blending amount of styrene as an aromatic vinyl monomer and the polymerization conversion rate in the step (1) were changed as shown in Table 1 and allyl methacrylate as a crosslinkable monomer was not blended.
  • a binder composition was prepared, and stability over time was evaluated.
  • polymerization can A and B was made to be the same as that of Example 1.
  • the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the amount of gas generation, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 4 Table 1 shows the blending amount of 2-ethylhexyl acrylate, which is a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher, blending amount of styrene, which is an aromatic vinyl monomer, and the polymerization conversion rate in step (1).
  • the binder composition was prepared in the same manner as in Example 1 except that 20 parts of butadiene was added as another monomer, and the stability over time was evaluated. In addition, even if it was a case where the compounding quantity of each component was changed, the ratio between the compounding quantities of each component contained in superposition
  • the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition.
  • the peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Table 1 shows the blending amount of 2-ethylhexyl acrylate, which is a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or more, blending amount of styrene, which is an aromatic vinyl monomer, and polymerization conversion rate in polymerization step 1. Except for changing as shown, a binder composition was prepared in the same manner as in Example 1, and stability over time was evaluated. In addition, even if it was a case where the compounding quantity of each component was changed, the ratio between the compounding quantities of each component contained in superposition
  • the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition.
  • the peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 6 A binder composition was prepared in the same manner as in Example 1 except that butyl acrylate was used in place of 2-ethylhexyl acrylate as a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher. evaluated. In addition, even if it was a case where the compounding quantity of each component was changed, the ratio between the compounding quantities of each component contained in superposition
  • Example 7 to 10 A binder composition was prepared in the same manner as in Example 1 except that sodium ascorbate, which is a reductone compound, was changed to the reductone compound shown in Table 1, and the stability over time was evaluated. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the lithium ion secondary battery. The results are shown in Table 1.
  • Example 1 except that the blending ratio of sodium ascorbate as a reductone compound was changed as shown in Table 1, and the blending ratio of tert-butyl hydroperoxide as a peroxide was changed as shown in Table 1.
  • a binder composition was prepared, and stability over time was evaluated.
  • the laminated cell battery type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 15 A binder composition was prepared in the same manner as in Example 1 except that the peroxide tert-butyl hydroperoxide was changed to benzoyl peroxide (BPO), and the stability over time was evaluated. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 1 Binder composition in the same manner as in Example 1 except that sodium ascorbate which is a reductone compound is not blended and the reaction is performed at 40 ° C. for 2 hours and then at 80 ° C. for 2 hours in Step (2). Were prepared and the stability over time was evaluated. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 2 A binder composition was prepared in the same manner as in Example 1 except that ethyl acrylate (EA) having a boiling point of 100 ° C. was used instead of 2-ethylhexyl acrylate which is a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher. Prepared and evaluated for stability over time. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • the mixture was stirred for about 120 minutes, and when the polymerization conversion rate (monomer consumption) reached 93%, distillation was performed under reduced pressure over 8 hours using an evaporator at 80 ° C. and 100 hPa (0.1 atm). It was. Thereafter, the mixture was cooled, a 5% aqueous sodium hydroxide solution was added to adjust the pH to 8, and an aqueous dispersion (binder composition) containing a desired particulate polymer was obtained. The obtained binder composition was evaluated for stability over time. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the lithium ion secondary battery. The results are shown in Table 1.
  • Example 4 A binder composition was prepared in the same manner as in Example 1 except that succinic acid was added instead of sodium ascorbate, which is a reductone compound, and stability over time was evaluated. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • Example 5 A binder composition was prepared in the same manner as in Example 1 except that the step (2) was carried out at a polymerization conversion rate of 81% in the step (1), and the temporal stability was evaluated. Moreover, the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition. The peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • step (2) was not performed.
  • step (1) the polymerization conversion rate in step (1) reached 93%
  • the mixture was cooled to 40 ° C., 0.3% by mass of ammonium persulfate (APS), which is a peroxide, was added, and the mixture was further reacted for 4 hours.
  • APS ammonium persulfate
  • 5% sodium hydroxide aqueous solution was added with respect to this aqueous dispersion, and it adjusted to pH8, and obtained the aqueous dispersion (binder composition) containing a desired particulate polymer.
  • the obtained binder composition was evaluated for stability over time.
  • the laminated cell type lithium ion secondary battery which has a negative electrode and this negative electrode was manufactured like Example 1 using the prepared binder composition.
  • the peel strength was evaluated for the negative electrode, and the gas generation amount, high-temperature storage characteristics, and high-temperature cycle characteristics were evaluated for the laminated cell type lithium ion secondary battery. The results are shown in Table 1.
  • the binder compositions of Examples 1 to 15 have good stability over time, and the negative electrode produced using such a binder composition has good peel strength. It can be seen that the secondary battery manufactured in this manner has a reduced gas generation amount and good high-temperature storage characteristics and high-temperature cycle characteristics.
  • Comparative Example 1 in which sodium ascorbate, which is a reductone compound, was not blended the residual amount of 2-ethylhexyl acrylate monomer in the obtained binder composition was large, and the temporal stability of the binder composition was low.
  • the stability of the binder composition is good, Although the peel strength of the negative electrode produced using the obtained binder is good and the amount of gas generated in the secondary battery is small, it can be seen that the high-temperature storage characteristics and the high-temperature cycle characteristics deteriorate. This is considered to be because the flexibility of the particulate polymer in the binder composition was lowered, and the binding property was lowered as the binder composition, which adversely affected the battery characteristics.
  • Example 1 and 3 it can be seen that the high-temperature storage characteristics and the high-temperature cycle characteristics of the secondary battery can be improved by using a crosslinkable monomer when forming the particulate polymer.
  • the peel strength of the negative electrode can be improved by adjusting the blending amount of the (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or more when forming the particulate polymer. I understand that.
  • Example 1 and Examples 7 to 10 it can be seen that all characteristics can be arranged in a high dimension by using ascorbic acid and its isomers, derivatives, and salts as reductone compounds.
  • Example 9 using ascorbyl palmitate, the gas generation amount, high-temperature storage characteristics, high-temperature cycle characteristics, and stability over time of the binder composition were inferior to Examples 1, 7, 8, and 10, but this This is because the molecular weight of ascorbyl palmitate is relatively large, and if it is added in the same amount as other ascorbic acid-based reductone compounds, the amount in terms of moles is reduced and the residual monomer reduction effect cannot be fully exhibited. It is thought that.
  • the amount of reductone compound and peroxide by adjusting the amount of reductone compound and peroxide, the amount of residual monomers can be sufficiently reduced, the amount of gas generated can be reduced, and high temperature storage characteristics and high temperature cycles can be achieved. It can be seen that the characteristics can be further improved.
  • the amount of sodium ascorbate, which is a reductone compound is relatively large, and it is considered that ascorbic acid remaining in the binder composition increases the gas generation amount.
  • the binder composition of the present invention was used for forming a positive electrode.
  • acrylonitrile as an ⁇ , ⁇ -unsaturated nitrile monomer 74.4 parts
  • 4.8 parts of sodium lauryl sulfate and 192 parts of ion-exchanged water as dispersants were added and stirred to prepare an emulsion.
  • This emulsion was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes. Thereafter, the mixture was stirred for about 120 minutes, and when the polymerization conversion rate (monomer consumption amount) reached 95%, it was cooled to 40 ° C.
  • the obtained particulate polymer had a glass transition temperature of ⁇ 38.0 ° C. and a volume average particle size of 0.11 ⁇ m.
  • the content ratio of (meth) acrylic acid ester monomer units having a boiling point of 145 ° C. or higher is 78%
  • the content ratio of acidic group-containing monomer units is 2%
  • ⁇ , ⁇ -unsaturated nitrile was 20%.
  • the content of the (meth) acrylic acid ester monomer (2-EHA) having a boiling point of 145 ° C. or higher with respect to 100 parts by mass of the particulate polymer was 208 ⁇ 10 ⁇ 6 parts by mass.
  • Co-Ni-Mn lithium composite oxide based active material product name: Cellseed NMC613, manufactured by Nippon Chemical Industry Co., Ltd .; hereinafter sometimes referred to as “NMC”
  • NMC Cellseed NMC613, manufactured by Nippon Chemical Industry Co., Ltd .
  • CMC sodium salt
  • aqueous solution of carboxymethyl cellulose as a viscosity modifier
  • the positive electrode slurry composition was applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 3 hours, and then roll pressed to obtain a positive electrode having a positive electrode mixture layer having a thickness of 50 ⁇ m.
  • slurry composition for negative electrode and negative electrode > 98 parts of graphite having a volume average particle diameter of 20 ⁇ m and a specific surface area of 4.2 m 2 / g as a negative electrode active material, and negative electrode binder BM-400B (40 of styrene-butadiene copolymer manufactured by Nippon Zeon Co., Ltd.) as a binder. (Mass% aqueous dispersion) is mixed with 1.0 part in solid content and 0.8 part in CMC with solid content. Further, water is added and mixed with a planetary mixer to obtain a slurry composition for negative electrode. Prepared. This negative electrode slurry composition was applied to one side of a 10 ⁇ m thick copper foil, dried at 110 ° C. for 3 hours, and then roll pressed to obtain a negative electrode having a negative electrode mixture layer having a thickness of 60 ⁇ m.
  • BM-400B 40 of styrene-butadiene copolymer manufactured by Nippon Zeon Co
  • a battery container was prepared using a laminate film made of an aluminum sheet and a polypropylene resin covering both surfaces thereof. Subsequently, the mixture layer was removed from the end portions of the positive electrode and the negative electrode obtained above to form a portion where the copper foil or the aluminum foil was exposed. A Ni tab was welded to the portion where the aluminum foil of the positive electrode was exposed, and a Cu tab was welded to the portion where the copper foil of the negative electrode was exposed. The obtained tabbed positive electrode and tabbed negative electrode were stacked with a separator made of a polyethylene microporous film interposed therebetween.
  • the direction of the surface of the electrode was such that the surface on the positive electrode mixture layer side and the surface of the negative electrode mixture layer side face each other.
  • the stacked electrode and separator were wound and stored in the battery container.
  • the electrolytic solution a solution prepared by dissolving LiPF 6 to a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 2 at 25 ° C. was used. .
  • the laminate film was sealed to produce a laminate cell type lithium ion secondary battery which is the lithium ion secondary battery of the present invention.
  • the amount of gas generation and high-temperature storage characteristics of the obtained laminated cell type lithium ion secondary battery were evaluated. The results are shown in Table 2.
  • the positive electrode obtained above was cut into a circle having a diameter of 13 mm.
  • the negative electrode obtained above was cut into a circle having a diameter of 14 mm.
  • a single-layer polypropylene separator (porosity 55%) produced by a dry method having a thickness of 25 ⁇ m was cut into a circle having a diameter of 18 mm. These were housed in a stainless steel coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm) provided with polypropylene packing.
  • the arrangement of the circular electrodes and separators in the outer container was as follows. The circular positive electrode was disposed so that the aluminum foil was in contact with the bottom surface of the outer container.
  • the circular separator was disposed so as to be interposed between the circular positive electrode and the circular negative electrode.
  • a full coin cell type lithium ion battery which is a lithium ion secondary battery of the present invention having a diameter of 20 mm and a thickness of about 3.2 mm, is sealed by covering with a stainless steel cap having a thickness of 0.2 mm and sealing the outer container.
  • a secondary battery (coin cell CR2032) was produced. The high-temperature cycle characteristics of the obtained full coin cell type lithium ion secondary battery were evaluated. The results are shown in Table 2.
  • Example 17 to 18 The blending amount of 2-ethylhexyl acrylate which is a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher and the blending amount of acrylonitrile which is an ⁇ , ⁇ -unsaturated nitrile monomer were changed as shown in Table 2, respectively. Except for this, a binder composition was prepared in the same manner as in Example 16, and the stability over time was evaluated. In addition, even if it was a case where the compounding quantity of each component was changed, the ratio between the compounding quantities of each component contained in superposition
  • Example 16 volume average particle diameter of the obtained particulate polymer was 0.11 ⁇ m as in Example 16. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 19 A binder composition was prepared in the same manner as in Example 16 except that n-butyl acrylate (boiling point 148 ° C.) was used as a (meth) acrylic acid ester monomer having a boiling point of 145 ° C. or higher, and the stability over time was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 20 to 23 A binder composition was prepared in the same manner as in Example 16 except that sodium ascorbate, which is a reductone compound, was changed to a reductone compound shown in Table 2, and the temporal stability was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 1 except that the blending ratio of sodium ascorbate as a reductone compound was changed as shown in Table 2, and the blending ratio of tert-butyl hydroperoxide as a peroxide was changed as shown in Table 2.
  • a binder composition was prepared in the same manner as in No. 16, and the stability over time was evaluated. Further, using the prepared binder composition, a laminated cell battery type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and high temperature storage characteristics were respectively obtained. In addition, the high-temperature cycle characteristics were evaluated. The results are shown in Table 2.
  • Example 28 A binder composition was prepared in the same manner as in Example 16 except that the peroxide tert-butyl hydroperoxide was changed to benzoyl peroxide (BPO), and the stability over time was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 7 Binder composition in the same manner as in Example 16 except that sodium ascorbate which is a reductone compound is not blended, and the reaction is performed at 40 ° C. for 2 hours and then at 80 ° C. for 2 hours in Step (2). Were prepared and the stability over time was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • a binder composition was prepared in the same manner as in Example 16 except that ethyl acrylate (EA) having a boiling point of 100 ° C. was used in place of 2-ethylhexyl acrylate which is a (meth) acrylic acid ester monomer, and was stable over time. Sex was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • acrylonitrile as an ⁇ , ⁇ -unsaturated nitrile monomer 74.4 parts
  • 4.8 parts of sodium lauryl sulfate and 192 parts of ion-exchanged water as dispersants were added and stirred to prepare an emulsion.
  • This emulsion was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes. Thereafter, the mixture was stirred for about 120 minutes, and when the polymerization conversion rate (monomer consumption) reached 95%, distillation was performed under reduced pressure over 8 hours using an evaporator at 80 ° C. and 100 hPa (0.1 atm). .
  • binder composition aqueous dispersion (binder composition) containing a desired particulate polymer was obtained.
  • the obtained binder composition was evaluated for stability over time. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 10 A binder composition was prepared in the same manner as in Example 16 except that succinic acid was added instead of sodium ascorbate, which is a reductone compound, and stability over time was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • Example 11 A binder composition was prepared in the same manner as in Example 16 except that the step (2) was carried out at a polymerization conversion rate of 80% in the step (1), and the temporal stability was evaluated. Further, using the prepared binder composition, a laminated cell type lithium ion secondary battery and a full coin cell type lithium ion secondary battery were produced in the same manner as in Example 16, and the gas generation amount and the high temperature storage characteristics were respectively obtained. As well as high temperature cycle characteristics. The results are shown in Table 2.
  • step (2) was not performed.
  • step (2) was not performed.
  • the polymerization conversion rate in step (1) reached 95%
  • the mixture was cooled to 40 ° C., 0.3% by mass of ammonium persulfate (APS) as a peroxide was added, and the reaction was further continued for 4 hours.
  • APS ammonium persulfate
  • 5% sodium hydroxide aqueous solution was added with respect to this aqueous dispersion, and it adjusted to pH8, and obtained the aqueous dispersion (binder composition) containing a desired particulate polymer.
  • the obtained binder composition was evaluated for stability over time.
  • the binder compositions of Examples 16 to 28 have good temporal stability, and the secondary battery produced using such a binder composition has a reduced amount of gas generation, high temperature storage characteristics and It can be seen that the high-temperature cycle characteristics are good.
  • Comparative Example 7 in which sodium ascorbate as a reductone compound was not blended, the residual amount of 2-ethylhexyl acrylate monomer in the obtained binder composition was large, and the stability of the binder composition with time was low. And it turns out that the gas generation amount of the secondary battery manufactured using this binder composition increases, and a high temperature storage characteristic and a high temperature cycling characteristic deteriorate remarkably.
  • the stability of the binder composition is good, Although the amount of gas generated in the secondary battery produced using the obtained binder is small, it can be seen that the high-temperature storage characteristics and the high-temperature cycle characteristics deteriorate. This is considered to be because the flexibility of the particulate polymer in the binder composition was lowered, and the binding property was lowered as the binder composition, which adversely affected the battery characteristics.
  • the compounding amounts of the redox initiator sodium ascorbate and Tert-butyl hydroperoxide
  • the unconverted monomer cannot be sufficiently polymerized in the redox polymerization, and the result It is considered that the residual monomer amount increases and the high-temperature storage characteristics and the high-temperature cycle characteristics deteriorate.
  • the temporal stability of the binder composition was good. The gas generation of the secondary battery is not a little, but the residual monomer amount in the binder composition cannot be sufficiently reduced, and the battery characteristics deteriorate.
  • ADVANTAGE OF THE INVENTION generation
  • a binder composition can be provided.
  • the slurry composition for secondary battery electrodes using the said binder composition can be provided.
  • the electrode for secondary batteries using the said slurry composition for secondary battery electrodes can be provided.

Abstract

L'objectif de la présente invention est de fournir une composition de liant pour des électrodes de batterie secondaire, qui possède une excellente stabilité à long terme et qui est apte à fournir une batterie secondaire dont la génération de gaz provoqué par des monomères résiduels est supprimée et qui possède de bonnes caractéristiques de stockage à haute température et des bonnes caractéristiques de cycle à haute température. Une composition de liant selon la présente invention contient un polymère particulaire, de l'eau et un composé de réductone et/ou une forme oxydée d'un composé de réductone. Le polymère particulaire est obtenu par polymérisation d'un mélange de monomère qui contient un monomère d'ester d'acide (méth)acrylique ayant un point d'ébullition de 145°C ou plus, et le rapport de teneur du monomère d'ester d'acide (méth)acrylique ayant un point d'ébullition de 145°C ou plus est de 1 x 10-6 parties par masse à 1 500 x 10-6 parties par masse (inclus) par rapport à 100 parties par masse du polymère particulaire.
PCT/JP2014/001852 2013-03-29 2014-03-28 Composition de liant pour électrodes de batterie secondaire, son procédé de fabrication, composition de bouillie pour électrodes de batterie secondaire, électrode pour batteries secondaires, et batterie secondaire WO2014156195A1 (fr)

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JP2015508095A JP6206484B2 (ja) 2013-03-29 2014-03-28 二次電池電極用バインダー組成物及びその製造方法、二次電池電極用スラリー組成物、二次電池用電極、並びに、二次電池

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WO2019054173A1 (fr) * 2017-09-15 2019-03-21 日本ゼオン株式会社 Composition de bouillie pour électrodes d'élément électrochimique, électrode pour éléments électrochimiques, élément électrochimique, et procédé de production de composition de bouillie pour électrodes d'élément électrochimique
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JP6996503B2 (ja) 2016-06-29 2022-01-17 日本ゼオン株式会社 非水系二次電池電極用バインダー組成物、非水系二次電池電極用スラリー組成物、非水系二次電池用電極および非水系二次電池
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JPWO2019181871A1 (ja) * 2018-03-23 2021-03-18 日本ゼオン株式会社 二次電池用バインダー組成物、二次電池電極用導電材ペースト、二次電池電極用スラリー組成物、二次電池電極用スラリー組成物の製造方法、二次電池用電極および二次電池
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CN115710149A (zh) * 2022-11-30 2023-02-24 西安近代化学研究所 一种dap-4为基的复合***粒子及其制备方法
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