Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
  • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
  • H01G11/38—Carbon pastes or blends; Binders or additives therein
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—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

Definitions

• the present invention is used for storage devices such as secondary batteries such as lithium ion secondary batteries and nickel hydrogen secondary batteries, electrochemical capacitors, etc., particularly non-aqueous electrolyte storage devices using non-aqueous electrolytes such as organic solvents as electrolytes.
• the present invention relates to a binder for an electrode, an electrode including the binder for an electrode, and a storage device including the electrode.
• BACKGROUND Storage devices such as lithium ion secondary batteries and electrochemical capacitors are used in electronic devices such as mobile phones, notebook computers, camcorders and the like.
• application to car applications such as electric vehicles and hybrid electric vehicles and storage batteries for household power storage has also been progressing due to rising awareness of environmental protection and maintenance of related laws.
• An electrode used for such a storage device is usually obtained by applying and drying an electrode material composed of an active material, a conductive support agent, a binder, and a solvent on a current collector.
• the binder is required to be excellent in binding property when used in an electrode and capable of imparting excellent electrical characteristics to an electricity storage device.
• Patent Document 1 proposes a new binder.
• binders having particularly excellent binding properties are required, and further studies are required.
• the present invention provides a binder that is excellent in binding property when used in an electrode, has excellent flexibility (flexibility), and is excellent in charge and discharge efficiency when used in an electric storage device. Intended to provide.
• the polymer contains a structural unit derived from a (meth) acrylic acid alkyl ester monomer and a structural unit derived from an ester monomer having an aromatic group.
• the present invention relates to the following.
• Item 1 Structural unit (A) derived from (meth) acrylic acid alkyl ester monomer
• the following general formula (1) (Wherein, R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 is an aromatic group which may have a substituent.)
• a polymer comprising a constituent unit (B) derived from the monomer represented by A binder for an electrode, comprising a polymer having a molar ratio of the constituent unit (A) to the constituent unit (B) in the polymer of 0.5 to 2.5.
• the structural unit (B) is represented by the following general formula (2) (Wherein, R 1 is hydrogen, or an alkyl group having 1 to 4 carbon atoms, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 is hydrogen And R 13 is an alkylene group having 1 to 3 carbon atoms, or a carbonyl group, R 14 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an aromatic group which may have a substituent.
• the binder for an electrode according to item 1 which is a constitutional unit derived from the monomer represented by Item 3 Furthermore, the following general formula (3): (Wherein, R 15 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, x is an integer of 2 to 8 and n is an integer of 2 to 30)
• item 1 or 2 containing the polymer containing the structural unit (C) derived from the monomer which has a hydroxyl group represented by these.
• Item 4 The binder for an electrode according to any one of Items 1 to 3, further comprising a polymer containing a structural unit (D) derived from a polyfunctional (meth) acrylate monomer having a functionality of 5 or less.
• Item 5 In the structural unit (D), the pentafunctional or lower polyfunctional (meth) acrylate monomer is represented by the following general formula (5): Wherein R 16 is the same or different and is a hydrogen atom or a methyl group, R 17 is a pentavalent or less organic group having 2 to 100 carbon atoms, and m is an integer of 5 or less. 5.
• the constituent unit (A) derived from a (meth) acrylic acid alkyl ester monomer is a constituent unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms
• An electrode material comprising the binder for an electrode according to any one of items 1 to 6.
• Item 10 The electrode material according to Item 9, wherein activated carbon is used as the active material.
• Item 11 The electrode material according to Item 9, wherein a silicon-based compound is used as the active material.
• a storage device comprising
• a binder for an electrode having excellent binding property when used for an electrode and having excellent flexibility and having excellent charge and discharge efficiency when used for an electricity storage device.
• a binder composition for an electrode including the binder for an electrode, an electrode material, an electrode, and an electricity storage device provided with the electrode.
• the binder for an electrode of the present invention has excellent binding properties.
• the binder for an electrode of the present invention is useful because excellent binding can be obtained when activated carbon is used as an active material in an electrode material.
• the binder for an electrode of the present invention can obtain particularly remarkable effects when a silicon-based compound is used as the active material used for the negative electrode.
• the volume change in charge and discharge is about 10% when using a carbon material, whereas when using a silicon-based compound, the capacity change by about 200% is accompanied by a capacity change due to charge and discharge cycles. It has the problem that the decline is large.
• the present invention has high bondability, excellent flexibility (flexibility), and high charge / discharge efficiency without losing the effect even when using a silicon compound as the active material used for the negative electrode. And low DC internal resistance, which is useful.
• the electricity storage device includes a secondary battery (a lithium ion secondary battery, a nickel hydrogen secondary battery, and the like) and an electrochemical capacitor.
• a secondary battery a lithium ion secondary battery, a nickel hydrogen secondary battery, and the like
• electrochemical capacitor a lithium ion secondary battery, a nickel hydrogen secondary battery, and the like
• (meth) acrylate means “acrylate or methacrylate”, and the same applies to expressions similar thereto.
• the binder for an electrode of the present invention is a structural unit (A) derived from a (meth) acrylic acid alkyl ester monomer, The following general formula (1) (Wherein, R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 is an aromatic group which may have a substituent.)
• a polymer comprising a constituent unit (B) derived from the monomer represented by A polymer is characterized in that the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is 0.5 to 2.5.
• the structural unit (A) is a structural unit derived from a (meth) acrylic acid alkyl ester monomer.
• the structural unit (A) is preferably a structural unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms, and a (meth) acrylic having an alkyl group having 1 to 8 carbon atoms
• a structural unit derived from an acid alkyl ester monomer is more preferable, and a structural unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 6 carbon atoms is further preferable, and a carbon number of 2 to 6
• the structural unit is derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group of 4.
• the preferred structural unit (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylic acid isobutyl, (meth) acrylic acid n-pentyl, (meth) acrylic acid isopentyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid isohexyl, (meth) acrylic acid n-heptyl, (meth) Examples include structural units derived from (meth) acrylic acid alkyl esters such as n-octyl acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate.
• the structural unit (A) may be of one type or of two or more types.
• the ratio of the structural unit (A) in the polymer is not particularly limited as long as the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is in the range of 0.5 to 2.5.
• the lower limit of the proportion of the structural unit (A) in the polymer is preferably 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 40 mol% or more.
• the upper limit of the ratio of the structural unit (A) in the polymer is preferably 75 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less. It is preferable at the point which the stability of an emulsion improves by setting it as this range.
• the structural unit (B) is represented by the following general formula (1) (Wherein, R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 is an aromatic group which may have a substituent.) Is a constitutional unit derived from
• the structural unit (B) is represented by the following general formula (2) (Wherein, R 1 is hydrogen, or an alkyl group having 1 to 4 carbon atoms, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 is hydrogen And R 13 is an alkylene group having 1 to 3 carbon atoms, or a carbonyl group, R 14 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an aromatic group which may have a substituent. It is preferable that it is an aromatic group which may have a substituent, q, r is an integer of 0 to 3, and s is an integer of 0 to 1. It is a constitutional unit derived from a monomer .
• R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or an alkyl group having 1 to 2 carbon atoms, and particularly preferably hydrogen or a methyl group.
• R 2 is an aromatic group which may have a substituent. Examples of substituents include alkyl groups, alkyl groups such as methyl, ethyl and isopropyl, unsaturated hydrocarbon groups such as vinyl, fluoro groups, halogeno groups such as chloro, bromo and iodo groups, amino groups, nitro groups and carboxyls. Groups and the like.
• the aromatic ring may have two or more.
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each have hydrogen, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, and a substituent It is preferably any one of an aromatic group which may be substituted, and is any one of hydrogen, a hydroxyl group, an alkyl group having 1 to 2 carbon atoms, and an aromatic group which may have a substituent.
• R 13 is an alkylene group having 1 to 3 carbon atoms, or a carbonyl group, and is preferably an alkylene group having 1 to 2 carbon atoms, or a carbonyl group.
• R 14 is an aromatic group which may have a substituent, and the aromatic group is preferably an aryl group, a benzyl group or a phenoxy group.
• substituents include alkyl groups, alkyl groups such as methyl, ethyl and isopropyl, unsaturated hydrocarbon groups such as vinyl, fluoro groups, halogeno groups such as chloro, bromo and iodo groups, amino groups, nitro groups and carboxyls. Groups and the like.
• the aromatic ring may have two or more.
• Each of q and r is an integer of 0 to 3, preferably an integer of 0 to 2, and preferably satisfies q + r ⁇ 1.
• s is an integer of 0 to 1.
• the preferred structural unit (B) include benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, 2- (meth) acrylate
• structural units derived from hydroxy-3-phenoxypropyl (meth) acrylic acid phenoxydiethylene glycol, neopentyl glycol- (meth) acrylic acid-benzoic acid ester, 2- (meth) acryloyloxyethyl-phthalic acid, etc.
• the structural unit (B) may be of one type or of two or more types.
• the ratio of the structural unit (B) in the polymer is not particularly limited as long as the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is in the range of 0.5 to 2.5.
• the lower limit of the ratio of the structural unit (B) in the polymer is preferably 20 mol% or more, more preferably 24 mol% or more, and particularly preferably 27 mol% or more.
• the upper limit of the ratio of the structural unit (B) in the polymer is preferably 60 mol% or less, more preferably 55 mol% or less, and particularly preferably 50 mol% or less.
• the molar ratio of the structural unit (A) to the structural unit (B) in the polymer (structural unit (A) mol / structural unit (B) mol) is preferably 0.5 or more, and 0.75
• the number is particularly preferably 1 or more, the number is preferably 2.5 or less, more preferably 2.2 or less, and particularly preferably 2 or less.
• the binder of the present invention has excellent binding property when used in an electrode, has excellent flexibility, and has excellent charge and discharge efficiency when used in an electricity storage device.
• R 15 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
• R 15 is a hydrogen atom or a methyl group.
• the monomer having a hydroxyl group is preferably a (meth) acrylate monomer (R 15 is a hydrogen atom or a methyl group).
• (C x H 2 x O) is a linear or branched alkyl ether group
• x is an integer of 2 to 8, preferably an integer of 2 to 7, and more preferably Is an integer of 2 to 6.
• n is an integer of 2 to 30, preferably an integer of 2 to 25, and more preferably an integer of 2 to 20.
• the structural unit (C) is preferably derived from the monomer having a hydroxyl group represented by the general formula (4) below.
• R 15 is a straight-chain or branched alkyl group having a hydrogen atom or a C 1 ⁇ 4
• o is an integer of 0 ⁇
• p is an integer of 0 ⁇ 30, o + p Is 2-30.
• o and p only represent the compositional ratio of the constituent unit, and it is possible to use a block of repeating units of (C 2 H 4 O) and a block of repeating units of (C 3 H 6 O).
• the repeating unit of (C 2 H 4 O) and the repeating unit of (C 3 H 6 O) are alternately or randomly arranged, or the random part and the block part are mixed. It may be a compound.
• R 15 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Preferably it is a hydrogen atom or a methyl group. That is, in the structural unit (C), the monomer having a hydroxyl group is preferably a (meth) acrylate monomer (R 15 is a hydrogen atom or a methyl group).
• o is an integer of 0 to 30
• p is an integer of 0 to 30
• o + p is 2 to 30
• o is an integer of 0 to 25
• p is 0 to 25
• o is preferably an integer of 2 to 25
• o is an integer of 0 to 20
• p is an integer of 0 to 20
• o + p is particularly preferably 2 to 20.
• hydroxyl group-containing monomer represented by the general formula (3) examples include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate.
• tetraethylene glycol mono (meth) acrylate tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate are preferable.
• the structural unit (C) may be of one type or of two or more types.
• the ratio is limited so that the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is in the range of 0.5 to 2.5. It is not particularly limited.
• the lower limit of the molar ratio of the structural unit (C) is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, and 2.0 mol% or more Particularly preferred.
• the upper limit of the ratio of the structural unit (C) in the polymer is preferably 15 mol% or less, more preferably 12 mol% or less, and particularly preferably 10 mol% or less.
• the structural unit (D) is preferably a structural unit derived from the following general formula (5).
• R 16 is the same or different and each is a hydrogen atom or a methyl group
• R 17 is an organic group having 2 to 100 carbon atoms having a valence of 5 or less
• m is an integer of 5 or less It is.
• m is preferably 2 to 5 (that is, a structural unit derived from a bifunctional to pentafunctional (meth) acrylate as the structural unit (D)), and 3 to 5 (that is, a structural unit More preferably, (D) is a structural unit derived from trifunctional to pentafunctional (meth) acrylate, and 3 to 4 (that is, structural unit (D) is derived from trifunctional to tetrafunctional (meth) acrylate) Particularly preferred is the structural unit).
• the structural unit derived from bifunctional (meth) acrylate in the structural unit (D) include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, dioxane glycol di (meth) acrylate, bis (meth) acryloyloxy
• the structural unit derived from bifunctional (meth) acrylates, such as ethyl phosphate, is mentioned.
• the structural unit derived from trifunctional (meth) acrylate in the structural unit (D) include trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, and trimethylolpropane PO-added tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 2,2,2-tris (meth) acryloyloxymethylethyl succinic acid, ethoxylated isocyanurate tri (meth) acrylate, ⁇ -caprolactone modified tris- (2-) Derived from trifunctional (meth) acrylates such as (meth) acryloxyethyl) isocyanurate, glycerin EO addition tri (meth) acrylate, glycerin PO addition tri (meth) acrylate and tris (meth) acryloyloxyethyl phosphate
• They include structural units that.
• structural units derived from a trifunctional (meth) acrylate selected from trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferable.
• structural unit derived from tetrafunctional (meth) acrylate in the structural unit (D) include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and pentaerythritol EO-added tetra (meth) acrylate And structural units derived from tetrafunctional (meth) acrylates such as
• structural units derived from pentafunctional (meth) acrylate include structural units derived from dipentaerythritol penta (meth) acrylate.
• the ratio is limited so that the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is in the range of 0.5 to 2.5. It is not particularly limited.
• the lower limit of the molar ratio of the structural unit (D) in the polymer is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and particularly preferably 0.2 mol% or more preferable.
• the upper limit of the ratio of the structural unit (D) is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 3 mol% or less.
• the structural unit (E) derived from the (meth) acrylic acid monomer in view of the improvement of the affinity to the active material when it is used for the electrode.
• the structural unit (E) which a polymer has may be one type, and may be two or more types.
• the ratio is limited so that the molar ratio of the structural unit (A) to the structural unit (B) in the polymer is in the range of 0.5 to 2.5 It is not particularly limited.
• the lower limit of the proportion of the structural unit (E) in the polymer is preferably 3 mol% or more, more preferably 4 mol% or more, and particularly preferably 5 mol% or more.
• the upper limit of the proportion of the structural unit (E) is preferably 15 mol% or less, more preferably 13 mol% or less, and particularly preferably 12 mol% or less.
• the polymer as structural units derived from other monomers besides the above, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, crotononitrile It can have a structural unit derived from a monomer selected from ⁇ -ethylacrylonitrile, ⁇ -cyanoacrylate, vinylidene cyanide and fumaronitrile.
• a general emulsion polymerization method As a method of obtaining a polymer, a general emulsion polymerization method, a soap-free emulsion polymerization method, etc. can be used. Specifically, a closed container equipped with a stirrer and a heating device is inert at room temperature and is inert to a composition containing a monomer, an emulsifier, a polymerization initiator, water, if necessary, a dispersant, a chain transfer agent, a pH adjuster, etc. The monomers and the like are emulsified in water by stirring under a gas atmosphere.
• a method of emulsification methods such as stirring, shearing, ultrasonic waves and the like can be applied, and a stirring blade, a homogenizer and the like can be used. Then, the temperature is raised while stirring to initiate polymerization, whereby a spherical polymer latex in which the polymer is dispersed in water can be obtained.
• the monomer addition method during polymerization may be monomer dropping, pre-emulsion dropping, etc. in addition to batch feeding, and two or more of these methods may be used in combination.
• pre-emulsion dropping refers to an addition method in which a monomer, an emulsifying agent, water and the like are previously emulsified in advance and the emulsion is dropped.
• the emulsifier used in the present invention is not particularly limited.
• the emulsifying agent is a surfactant, and the surfactant includes a reactive surfactant having a reactive group.
• Nonionic surfactants and anionic surfactants which are generally used in the emulsion polymerization method can be used.
• nonionic surfactant for example, polyoxyethylene alkyl ether, polyoxyethylene alcohol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene
• examples thereof include fatty acid esters and polyoxyethylene sorbitan fatty acid esters
• examples of the reactive nonionic surfactants include Latemul PD-420, 430, 450 (manufactured by Kao Corporation), Adekaria Soap ER (manufactured by Adeka), Aqualon. RN (made by Dai-ichi Kogyo Seiyaku Co., Ltd.), Antox LMA (made by Nippon Emulsifier), Antox EMH (made by Nippon Emulsifier), etc. are mentioned.
• anionic surfactant examples include metal salts of sulfuric acid ester type, carboxylic acid type or sulfonic acid type, ammonium salts, triethanol ammonium salts, surfactants of phosphoric acid ester type and the like.
• the sulfuric acid ester type, the sulfonic acid type and the phosphoric acid ester type are preferable, and the sulfuric acid ester type is particularly preferable.
• anionic surfactants of sulfuric acid ester type include metal alkyl sulfates such as dodecyl sulfate, ammonium, or alkyl sulfate triethanolamine, polyoxyethylene dodecyl ether sulfate, polyoxyethylene isodecyl ether sulfate, polyoxyethylene Examples thereof include metal salts of polyoxyethylene alkyl ether sulfuric acid such as tridecyl ether sulfuric acid, ammonium salts, and triethanolamine etc.
• Latemul PD-104, 105 manufactured by Kao Corporation
• Adekaria Soap SR manufactured by Adeka
• Aqualon HS manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• Aqualon KH manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• sodium dodecyl sulfate, ammonium dodecyl sulfate, triethanolamine dodecyl sulfate, sodium dodecyl benzene sulfonate, Latem PD-104 and the like can be mentioned.
• nonionic surfactants and / or anionic surfactants may be used.
• the reactivity of the reactive surfactant means that it contains a reactive double bond and undergoes a polymerization reaction with the monomer during polymerization. That is, the reactive surfactant acts as an emulsifier for the monomer during polymerization for producing the polymer, and after polymerization, it is covalently bonded to a part of the polymer to be incorporated. Therefore, the emulsion polymerization and the dispersion of the produced polymer are good, and the physical properties (flexibility, binding property) as a binder for an electrode are excellent.
• the amount of the constituent unit of the emulsifier may be an amount generally used in the emulsion polymerization method. Specifically, it is in the range of 0.01 to 25% by mass, preferably 0.05 to 20% by mass, and more preferably 0.1 to 20% by mass, based on the amount of monomers (100% by mass) of the charge. It is.
• the polymerization initiator used in the present invention is not particularly limited, and polymerization initiators generally used in the emulsion polymerization method and suspension polymerization method can be used. Preferably, it is an emulsion polymerization method. In the emulsion polymerization method, a water-soluble polymerization initiator is used, and in the suspension polymerization method, an oil-soluble polymerization initiator is used.
• water-soluble polymerization initiator examples include water-soluble polymerization initiators represented by persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, 2-2′-azobis [2- (2) -Imidazolin-2-yl) propane], or a hydrochloride or sulfate thereof, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2- Methylpropanamidine), or a hydrochloride or sulfate thereof, 3,3 ′-[azobis [(2,2-dimethyl-1-iminoethane-2,1-diyl) imino]] bis (propanoic acid), 2,2 Preferred are polymerization initiators of water-soluble azo compounds such as'-[azobis (dimethylmethylene)] bis (2-imidazoline).
• persulfates such as potassium persulfate, sodium persulfate and ammoni
• oil-soluble polymerization initiators examples include cumene hydroperoxide, benzoyl peroxide, organic peroxides such as acetyl peroxide and t-butyl hydroperoxide, azobisisobutyronitrile, 1,1'-azobis (cyclohexane Preferred are polymerization initiators of oil-soluble azo compounds such as carbonitriles) and redox initiators. These polymerization initiators may be used alone or in combination of two or more.
• the amount of polymerization initiator used may be an amount generally used in emulsion polymerization or suspension polymerization. Specifically, it is in the range of 0.01 to 10% by mass, preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass, with respect to the amount of monomer (100% by mass) to be charged. It is.
• Chain transfer agents can be used as needed.
• specific examples of the chain transfer agent include alkyl mercaptan such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and n-stearyl mercaptan, and 2,4-diphenyl-4.
• Xanthogen compounds such as -methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, dimethylxanthogen disulfide, diisopropyl xanthogen disulfide, terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram mono Thiuram compounds such as sulfide, phenol compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol Halogenated hydrocarbon compounds such as ololmethane, dibromomethane and carbon tetrabromide, ⁇ -benzyloxystyrene, vinyl ethers such as ⁇ -benzyloxyacrylonitrile and ⁇ -benzyloxyacrylamide, triphenylethane, pentaphenylethane, acrolein and meth
• the polymerization temperature and the polymerization time are not particularly limited.
• the temperature can be appropriately selected depending on the type of polymerization initiator to be used, etc., but generally, the polymerization temperature is 20 to 100 ° C., and the polymerization time is 0.5 to 100 hours.
• the binder for an electrode of the present invention has a polymer, but water or other substance such as an emulsifier may be contained in the inside of the polymer or attached to the outside.
• the amount of the substance contained inside or attached to the outside is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass with respect to 100 parts by mass of the polymer. It is particularly preferred that
• Binder composition for electrode> The binder composition for an electrode of the present invention contains the binder for an electrode of the present invention described in the section of "1. binder for an electrode” described above together with a solvent, and the binder for an electrode is dispersed in a solvent. May be there.
• the solvent may be water or an organic solvent.
• Organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, alcohols such as amyl alcohol, acetone, methyl ethyl ketone, Ketones such as cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, dioxane, and tetrahydrofuran, amide-based polar organic compounds such as N, N-dimethylformamide, N-methyl-2-pyrrolidone (NMP) Examples thereof include solvents, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ortho-dichlorobenzene, and para-dichlorobenzen
• the binder composition for electrodes of the present invention is preferably an aqueous binder composition in which the binder for electrodes is dispersed in water.
• the binder composition for electrodes of the present invention may be an emulsion using an emulsion produced in obtaining a polymer.
• the content of the binder for the electrode in the binder composition for an electrode of the present invention is not particularly limited, but the content of the binder for the electrode is preferably 0.2 to 80% by mass, preferably 0.5
• the content is more preferably 70 to 70% by mass, and particularly preferably 0.5 to 60% by mass.
• the solid content of the binder composition is generally considered to be a polymer and an emulsifier (only when the polymer is used in emulsion polymerization).
• the binder composition for electrodes of the present invention can adjust pH by using a base as a pH adjuster as needed.
• a base include alkali metal (Li, Na, K, Rb, Cs) hydroxide, ammonia, an inorganic ammonium compound, an organic amine compound and the like.
• the pH range is pH 2-11, preferably pH 3-10, more preferably pH 4-9.
• Electrode material contains at least an active material and the binder for an electrode of the present invention described in the section of “1. Binder for electrode” described above, and may further contain a conductive auxiliary. In the production of the electrode material of the present invention, the binder composition for an electrode of the present invention described in the section of "2. Binder composition for electrode” containing the binder for an electrode of the present invention together with a solvent can also be used.
• the positive electrode material used for the positive electrode contains a positive electrode active material and the binder for an electrode of the present invention, and may further contain a conductive aid, and a negative electrode material used for the negative electrode
• the binder for an electrode according to the present invention may further contain a conductive auxiliary agent, in an electric double layer capacitor (electrochemical capacitor), as a positive electrode material used for the positive electrode as an active material
• An active carbon and the binder for an electrode according to the present invention may be contained, and a conductive auxiliary may be further contained.
• a negative electrode material used for the negative electrode contains active carbon as an active material and the binder for an electrode according to the present invention It may contain an agent.
• the positive electrode active material used in the lithium ion battery is an alkali metal-containing composite oxide having a composition of any of AMO 2 , AM 2 O 4 , A 2 MO 3 , and AMBO 4 .
• A may be an alkali metal
• M may be a single or two or more transition metals, and part of them may include non-transition metals.
• B consists of P, Si or a mixture thereof.
• the positive electrode active material is preferably a powder, and the particle diameter thereof is preferably 50 microns or less, more preferably 20 microns or less. These active materials have an electromotive force of 3 V (vs. Li / Li +) or more.
• more preferable positive electrode active materials are, specifically, Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x CrO 2 , Li x Co a Ni 1 -a O 2 , Li x Mn a Ni 1 -a O 2 , Li x Co b Mn c Ni 1 -bc O 2 , Li x Ni a Co b Al c O 2 , Li x Mn 2 O 4 , Li y MnO 3 , Li y Mn e Fe 1-e O 3 , Li y Mn e Ti 1-e O 3 , Li x CoPO 4 , Li x MnPO 4 , Li x NiPO 4 , Li x FePO 4 , Li Mention may be made of x Mn f Fe 1-f PO 4 .
• a negative electrode active material used for a lithium ion battery a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (porous structure) capable of absorbing and desorbing lithium ions, or absorbing and desorbing lithium ions It is a powder composed of metals such as possible lithium, aluminum-based compounds, tin-based compounds, silicon-based compounds and titanium-based compounds.
• the particle diameter is preferably 10 nm or more and 100 ⁇ m or less, and more preferably 20 nm or more and 20 ⁇ m or less.
• the negative electrode active material has a porosity of about 70%.
• Examples of the silicon-based compound include elements Si, alloys with Si, oxides containing Si, carbides containing Si, etc. Si, SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2, NiSi 2, CaSi 2 , CrSi 2, Cu 5 Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO x (0 ⁇ x ⁇ 2), SnSiO x , LiSiO can be exemplified, and SiO x (0 ⁇ x ⁇ 2) is preferable, and silicon monoxide (SiO) or the like.
• the lower limit of the content of the silicon-based compound to the total amount (100% by mass) of the active material is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass or more
• the upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less.
• the binder of the present invention when a silicon-based compound is used as the active material used for the negative electrode, it is preferable to use a carbon material as the active material in combination.
• carbon materials graphite, low crystalline carbon (soft carbon, hard carbon), carbon black (ketjen black, acetylene black, channel black, lamp black, oil furnace black, thermal black etc.), fullerene, carbon nanotube, carbon Carbon materials such as nanofibers, carbon nanohorns and carbon fibrils can be exemplified, and graphite is preferable.
• the lower limit of the content of the carbon material to the total amount (100% by mass) of the active material is preferably 20% by mass or more, more preferably 40% by mass or more, and particularly preferably 60% by mass or more.
• the upper limit is preferably 99% by mass or less, more preferably 98% by mass or less, and particularly preferably 96% by mass or less.
• activated carbon As an active material used for an electric double layer capacitor (electrochemical capacitor), activated carbon can be illustrated.
• activated carbon refers to activated carbide, and commercially available activated carbon may be used, or activated carbon produced according to a known method may be used.
• the activated carbon can be obtained by carbonizing raw materials such as wood, coconut shell, pulp waste solution, coal, heavy oil, phenol resin and the like, and activating the obtained carbide.
• the activation may be a known activation method and can be performed by a gas activation method or a chemical activation method.
• the carbide is activated by being brought into contact with a gas such as water vapor, carbon dioxide gas or oxygen under heating.
• the chemical activation method the carbide is activated by heating in a state of being in contact with a known activating agent.
• activating agents include zinc chloride, phosphoric acid, and / or alkali compounds (such as metal hydroxides such as sodium hydroxide). It is preferable to use activated carbon activated with steam (denoted as steam activated carbon in the present application) and / or activated carbon activated with alkali (denoted as alkali activated carbon in the present application).
• the content of the active material in the electrode material is not particularly limited, and is, for example, about 99.9 to 50% by mass with respect to the electrode material (100% by mass) excluding components for forming a slurry such as water, More preferably, about 99.5 to 70% by mass, and still more preferably about 99 to 85% by mass.
• One type of active material may be used alone, or two or more types may be used in combination.
• conductive aid When using a conductive aid, known conductive aids can be used, and conductive carbon blacks such as graphite, furnace black, acetylene black and ketjen black, carbon fibers such as carbon nanotubes, metal powder, etc. It can be mentioned. These conductive aids may be used alone or in combination of two or more.
• the content of the conductive auxiliary is not particularly limited, but preferably 20 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the active material.
• a conductive support agent is contained in positive electrode material, as a lower limit of content of a conductive support agent, 0.05 mass part or more, 0.1 mass part or more, 0.2 mass part or more, 0 normally .5 parts by mass or more, 2 parts by mass or more can be exemplified.
• the electrode material of the present invention may optionally contain a thickener.
• the type of the thickener is not particularly limited, but preferred are sodium salts of cellulose compounds, ammonium salts, polyvinyl alcohol, polyacrylic acid and salts thereof and the like.
• sodium salts or ammonium salts of the cellulose-based compounds include sodium salts or ammonium salts of alkylcelluloses in which a cellulose-based polymer is substituted by various derivative groups. Specific examples thereof include methylcellulose, methylethylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose (CMC), ammonium salt, triethanolammonium salt and the like. Particularly preferred is the sodium or ammonium salt of carboxymethylcellulose.
• One of these thickeners may be used alone, or two or more thereof may be used in combination in any ratio.
• the content of the thickener is not particularly limited, but preferably 5 parts by mass or less, more preferably 3 parts by mass or less, with respect to 100 parts by mass of the active material.
• a thickener is contained, as a lower limit of content of a thickener, normally 0.05 mass part or more, 0.1 mass part or more, 0.2 mass part or more, 0.5 mass part Above, 1 mass part or more can be illustrated.
• the electrode material of the present invention may contain water to form a slurry.
• Water is not particularly limited, and generally used water can be used. Specific examples thereof include tap water, distilled water, ion exchanged water, and ultrapure water. Among them, preferred are distilled water, ion exchange water, and ultrapure water.
• the solid content concentration of the slurry is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 20 to 80% by mass. Being particularly preferred.
• the ratio of the amount of polymer in the solid content of the slurry is preferably 0.1 to 15% by mass, and 0.2 to 10% by mass. Is more preferable, and 0.3 to 7% by mass is particularly preferable.
• the preparation method of the electrode material is not particularly limited, and the positive electrode active material or the negative electrode active material, the binder for the electrode of the present invention, the conductive additive, water and the like can be used as usual stirrers, dispersers, kneaders, planetary ball mills, homogenizers, etc. It may be used and dispersed. In order to increase the efficiency of dispersion, heating may be performed in a range that does not affect the material.
• Electrode> The electrode of the present invention is characterized by including the electrode material of the present invention described in the above-mentioned section "3. Electrode material" and a current collector. The details of the electrode material of the present invention are as described above.
• a known current collector can be used for the electrode of the present invention.
• the positive electrode metals such as aluminum, nickel, stainless steel, gold, platinum, titanium and the like are used.
• the negative electrode metals such as copper, nickel, stainless steel, gold, platinum, titanium and aluminum are used.
• the method for producing the electrode is not particularly limited, and a general method may be used. It is carried out by uniformly applying a battery material to a suitable thickness on the surface of a current collector (metal electrode substrate) by a doctor blade method, an applicator method, a silk screen method or the like.
• the thickness is made uniform by a blade having a predetermined slit width.
• the electrode is dried, for example, in a hot air at 100 ° C. or in a vacuum at 80 ° C. in order to remove excess organic solvent and water.
• An electrode material is manufactured by press-molding the electrode after drying with a press apparatus. After pressing, heat treatment may be performed again to remove water, solvents, emulsifiers and the like.
• the electricity storage device of the present invention is characterized by including the positive electrode, the negative electrode, and the electrolytic solution described in the section of “4. Electrode” described above. That is, the electrode used for the electrical storage device of the present invention contains the electrode material of the present invention, that is, the binder for the electrode of the present invention. The details of the electrode of the present invention are as described above. In addition, about the electrical storage device of this invention, the electrode using the electrode material containing the binder for electrodes of this invention should just be used for at least one of a positive electrode and a negative electrode, and the binder for electrodes of this invention is included. A known electrode can be used for the electrode not using the electrode material.
• the electrolyte is not particularly limited, and a known electrolyte can be used.
• a specific example of the electrolytic solution includes a solution containing an electrolyte and a solvent.
• the electrolyte and the solvent may be used alone or in combination of two or more.
• a lithium salt compound can be exemplified. Specifically, LiBF 4 , LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2) ) 2, LiN etc. [CF 3 SC (C 2 F 5 SO 2) 3] 2 , and the like, but not limited thereto.
• electrolytes other than lithium salt compounds examples include tetraethyl ammonium tetrafluoroborate, triethyl monomethyl ammonium tetrafluoroborate, tetraethyl ammonium hexafluorophosphate and the like.
• the organic solvent or a normal temperature molten salt can be illustrated.
• organic solvent examples include an aprotic organic solvent, and specifically, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane ⁇ -butyrolactone, tetrahydrofuran, 1,3-dioxolane, dipropyl carbonate, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propyl nitrile, anisole, acetate, propionate, diethyl ether and the like linear ethers And two or more types may be mixed and used.
• propylene carbonate ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane ⁇ -butyrolactone, tetrahydrofuran, 1,3-dioxolane,
• the room temperature molten salt is also called an ionic liquid, and is a "salt" composed only of ions (anion, cation), and in particular, a liquid compound is called an ionic liquid.
• the room temperature molten salt in the present invention refers to a salt in which at least a part is liquid at normal temperature
• the normal temperature refers to a temperature range in which the battery is generally assumed to operate.
• the upper limit of the temperature range in which the battery normally operates is about 120 ° C., sometimes about 80 ° C., and the lower limit is about ⁇ 40 ° C., sometimes about ⁇ 20 ° C.
• quaternary ammonium organic cations As cationic species of the molten salt at room temperature, quaternary ammonium organic cations of pyridine type, aliphatic amine type and alicyclic amine type are known. Examples of quaternary ammonium organic cations include imidazolium ions such as dialkyl imidazolium and trialkyl imidazolium, tetraalkyl ammonium ions, alkyl pyridinium ions, pyrazolium ions, pyrrolidinium ions and piperidinium ions. In particular, imidazolium ion is preferred.
• tetraalkyl ammonium ion examples include trimethylethyl ammonium ion, trimethylethyl ammonium ion, trimethylpropyl ammonium ion, trimethylhexyl ammonium ion, tetrapentyl ammonium ion, triethyl methyl ammonium ion and the like, but are limited thereto. is not.
• alkyl pyridinium ion N-methyl pyridinium ion, N-ethyl pyridinium ion, N-propyl pyridinium ion, N-butyl pyridinium ion, 1-ethyl-2-methyl pyridinium ion, 1-butyl-4-methyl pyridinium
• the ion include 1-butyl-2,4 dimethyl pyridinium ion and the like, but not limited thereto.
• imidazolium ion 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1- Butyl-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl- Examples include 2,3-dimethylimidazolium ion and the like, but not limited thereto.
• the anion species of the molten salt at room temperature include chloride ion, bromide ion, halide ion such as iodide ion, perchlorate ion, thiocyanate ion, tetrafluoroborate ion, nitrate ion, AsF 6 ⁇ , PF 6 ⁇
• Inorganic acid ion such as stearyl sulfonate ion, octyl sulfonate ion, dodecylbenzene sulfonate ion, naphthalene sulfonate ion, dodecyl naphthalene sulfonate ion, 7,7,8,8-tetracyano-p-quinodimethane ion etc
• a normal temperature molten salt may be used individually by 1 type, and may be used combining 2 or more types.
• additives can be used in the electrolytic solution as required.
• the additive include flame retardants, flame retardants, positive electrode surface treatment agents, negative electrode surface treatment agents, and overcharge inhibitors.
• Flame retardants and flame retardants include brominated epoxy compounds, phosphazene compounds, halides such as tetrabromo bisphenol A, chlorinated paraffin, etc., antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, phosphoric acid ester, polyphosphate Examples include acid salts and zinc borate.
• the positive electrode surface treatment agent include inorganic compounds such as carbon and metal oxides (MgO, ZrO 2 and the like) and organic compounds such as ortho-terphenyl and the like.
• the negative electrode surface treatment agent include vinylene carbonate, fluoroethylene carbonate, polyethylene glycol dimethyl ether and the like.
• the overcharge inhibitor include biphenyl and 1- (p-tolyl) adamantane.
• the method for producing the electricity storage device of the present invention is not particularly limited, and is produced by a known method using a positive electrode, a negative electrode, an electrolytic solution, a separator and the like as needed.
• a positive electrode for example, in the case of coin type, the positive electrode, the separator if necessary, and the negative electrode are inserted into the outer can. Electrolyte is put into this and impregnated. Thereafter, the sealing body is joined to the sealing body by tab welding or the like, and the sealing body is sealed and crimped to obtain an electric storage device.
• the shape of the storage device is not limited, examples thereof include coin, cylinder, and sheet.
• the separator prevents the positive electrode and the negative electrode from being in direct contact with each other to short-circuit in the storage battery, and a known material can be used.
• Specific examples of the separator include porous polymer films such as polyolefin and paper.
• porous polymer film films of polyethylene, polypropylene and the like are preferable because they are less affected by the electrolytic solution.
• the binding test was conducted by a 180 ° peel test. Specifically, cut the electrode into a width 2 cm ⁇ length 5 cm, affix a tape (adhesive tape: made by Nichiban, width 1.8 cm, length 5 cm), and make one end of the electrode in the longitudinal direction a strograph E3-L While fixed, the tape was peeled off at a test speed of 50 mm / min and a load range of 5 N in the direction of 180 °. The test was conducted three times and the weighted average value was determined. The evaluation results are summarized in Tables 2 and 3.
• the bending test was performed by a mandrel bending test. Specifically, cut the electrode into 3 cm wide x 8 cm long, support the stainless steel rod 4 mm in diameter at the center side (4 cm portion) in the longitudinal direction (with the electrode surface facing outward) 180 ° The state of the coating film at the bent portion when bent was observed. Measured five times by this method, and no cracking or peeling of the electrode surface or peeling from the current collector occurred at all five times ⁇ , one or more cracks or peeling at one time x It was evaluated. The evaluation results are summarized in Tables 2 and 3.
• the coin battery was subjected to constant current charging at 1 C and charged to 2.7 V, and then 0.05 C constant voltage charging was performed. After charging, the battery was rested for 10 minutes. Finally, a constant current discharge at 1 C was performed to discharge to 1.5 V. The discharge capacity at 1 C was divided by the charge capacity to obtain a percentage, which was taken as the charge / discharge efficiency (%).
• the evaluation results are summarized in Table 2 and shown.
• ⁇ Measurement of average particle size The average particle size of the polymer was measured under the following conditions.
• Particle size distribution measuring device using dynamic light scattering Zetasizer Nano (Spectris Corporation) (Measurement condition) 1. 50 ⁇ L of the synthesized emulsion solution is sampled. 2. The sampled emulsion solution is diluted by adding 700 ⁇ L of ion-exchanged water three times. 3. Remove 2100 ⁇ L of solution from the dilution solution. 4. Add and dilute 700 ⁇ L ion-exchanged water to the remaining 50 ⁇ L sample and measure.
• the aggregates of the polymer were measured as follows.
• the polymerized emulsion solution is filtered using a 150 mesh stainless steel wire mesh (Kansai Wire Mesh Co., Ltd.) to scrape off the aggregates adhering to the stirring blade and the beaker. Thereafter, the collected aggregate is washed with ion exchanged water, dried for 24 hours, and the mass of the aggregate is measured. The measured amount of aggregates is divided by the emulsion yield to obtain the amount of aggregates (% by mass).
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.3 to 7.8 using a 28% aqueous ammonia solution, and the binder composition A (polymerization conversion ratio 99% or more, solid content concentration 40.3 wt%) which is an emulsion solution And the amount of aggregation: 0.05% by mass). The average particle size of the obtained polymer was 0.118 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• Examplementation Example 2 In the beaker, 771.43 mmol of acrylic acid, 402.00 mmol of phenoxyethyl methacrylate, 36.18 mmol of acrylic acid, 86.16 mmol of methacrylic acid, 40.20 mmol of polyethylene glycol monomethacrylate (manufactured by NOF Corporation: Blenmer PE-90), Add 4.02 mmol of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-TMPT), 2.00 g of sodium dodecyl sulfate as an emulsifier, 300 g of ion exchanged water, and 0.24 g of ammonium persulfate as a polymerization initiator, using an ultrasonic homogenizer The mixture was sufficiently stirred to form a milky lotion.
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.5 to 7.7 using a 28% aqueous ammonia solution, and a binder composition B (polymerization conversion ratio 99% or more, solid content concentration 40.2 wt%) which is an emulsion solution And the amount of aggregation: 0.03% by mass). The average particle size of the obtained polymer was 0.250 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.5 to 7.7 using a 28% aqueous ammonia solution, and a binder composition C as an emulsion solution (polymerization conversion rate 97% or more, solid content concentration 39.1 wt% And the amount of aggregation: 0.12% by mass). The average particle size of the obtained polymer was 0.134 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• Examplementation Example 4 In a beaker, 634.14 mmol of 2-ethylhexyl acrylate, 330.45 mmol of phenoxyethyl methacrylate, 29.74 mmol of acrylic acid, 70.83 mmol of methacrylic acid, 33.05 mmol of polyethylene glycol monomethacrylate (manufactured by NOF Corporation: Brenmer PE-90), 3.30 mmol of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-TMPT), 2.00 g of sodium dodecyl sulfate as an emulsifier, 300 g of ion exchange water and 0.24 g of ammonium persulfate as a polymerization initiator, using an ultrasonic homogenizer The mixture was sufficiently stirred to form a milky lotion.
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.4 to 7.8 using a 28% aqueous ammonia solution, and a binder composition D as an emulsion solution (polymerization conversion ratio 99% or more, solid content concentration 39.7 wt% And the amount of aggregation: 0.03% by mass). The average particle size of the obtained polymer was 0.109 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.3 to 7.8 using a 28% aqueous ammonia solution, and the binder composition E which is an emulsion solution (polymerization conversion rate 97% or more, solid content concentration 39.0 wt% And the amount of aggregation: 0.08% by mass). The average particle size of the obtained polymer was 0.246 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution was adjusted to 2.4 to 7.8 using a 28% aqueous ammonia solution to obtain a binder composition F as an emulsion solution, but the polymer separated and no emulsion was obtained. .
• the reaction container equipped with a stirrer was heated to 55 ° C. in a nitrogen atmosphere, and the emulsion was added over 2 hours. After the addition of the emulsion, it was further polymerized for 1 hour and then cooled. After cooling, the pH of the polymerization solution is adjusted to 2.5 to 7.8 using a 28% aqueous ammonia solution, and a binder composition G (polymerization conversion ratio 94% or more, solid content concentration 37.9 wt%) which is an emulsion solution And the amount of aggregation: 0.56% by mass). The average particle size of the obtained polymer was 0.130 ⁇ m. The molar ratio (mol%) in the polymer is shown in Table 1.
• Example 3 85 parts by mass of activated carbon as an active material, 5 parts by mass of acetylene black as a conductive additive, 2 parts by mass of sodium salt of carboxymethyl cellulose, and 4 parts by mass of the binder composition A obtained in Practical Example 1 of the binder composition Parts were added, water was further added so that the solid content concentration of the slurry was 24% by mass, and the mixture was sufficiently mixed using a planetary mill to obtain a slurry.
• the obtained slurry is applied on a 20 ⁇ m thick aluminum current collector using a 100 ⁇ m gap baker applicator, pressed with a roll press, and dried at 150 ° C. for 12 hours or more in a vacuum state. An 89 ⁇ m electrode was produced.
• the evaluation results of the adhesion test and the bending test are shown in Example 1 of Table 2.
• Example 1 Active material 89 parts by mass of activated carbon, 5 parts by mass of acetylene black as a conductive auxiliary agent, 2 parts by mass of sodium salt of carboxymethylcellulose, 4 parts by mass of the binder composition B obtained in Practical Synthesis Example 2 of the binder composition Parts were added and water was further added so that the solid content concentration of the slurry was 24% by mass, and the mixture was sufficiently mixed using a planetary mill to obtain a slurry in the same manner as in Example 1 of the electrode. Made. The thickness of the obtained electrode was 85 ⁇ m. The evaluation results of the adhesion test and the bending test are shown in Example 2 of Table 2.
• Example 1 Active material 89 parts by mass of activated carbon, 5 parts by mass of acetylene black as a conductive aid, 2 parts by mass of sodium salt of carboxymethylcellulose, 4 parts by mass of the binder composition C obtained in Practical Example of Binder Composition 3 Parts were added, water was further added so that the solid content concentration of the slurry was 22 mass%, and the slurry was obtained by sufficiently mixing using a planetary mill in the same manner as in Example 1 of the electrode. Made. The thickness of the obtained electrode was 96 ⁇ m. The evaluation results of the adhesion test and the bending test are shown in Example 3 of Table 2.
• Example 4 of practical preparation of electrode Example 1 Active material 89 parts by mass of activated carbon, 5 parts by mass of acetylene black as a conduction aid, 2 parts by mass of sodium salt of carboxymethylcellulose, 4 parts by mass of the binder composition D obtained in Practical Synthesis Example 4 of the binder composition Parts were added, water was further added so that the solid content concentration of the slurry was 22 mass%, and the slurry was obtained by sufficiently mixing using a planetary mill in the same manner as in Example 1 of the electrode. Made. The thickness of the obtained electrode was 88 ⁇ m. The evaluation results of the adhesion test and the bending test are shown in Example 4 of Table 2.
• Example of practical preparation of electrode 5-1 92 parts by mass of graphite as an active material, 5 parts by mass of SiO, 0.5 parts by mass of acetylene black as a conductive additive, 1.8 parts by mass of sodium salt of carboxymethyl cellulose, and Example of binder composition 0.7 mass part is added as solid content of the binder composition E, water is further added so that solid content concentration of a slurry may be 50.5 mass%, and it mixes thoroughly using a planetary mixer, and obtains a slurry.
• the binder composition E 92 parts by mass of graphite as an active material, 5 parts by mass of SiO, 0.5 parts by mass of acetylene black as a conductive additive, 1.8 parts by mass of sodium salt of carboxymethyl cellulose, and Example of binder composition 0.7 mass part is added as solid content of the binder composition E, water is further added so that solid content concentration of a slurry may be 50.5 mass%, and it mixes thoroughly using a planetary mixer, and obtains a slurry
• the obtained slurry is applied on a 20 ⁇ m thick aluminum current collector using a 100 ⁇ m gap baker applicator, pressed with a roll press, and dried at 110 ° C. for 12 hours or more in a vacuum state. An electrode of 37 ⁇ m was produced.
• the evaluation results of the adhesion test and the bending test are shown in Example 5-1 of Table 3.
• Example of Implementation Preparation of Electrode 5-2 87 parts by mass of graphite as an active material, 10 parts by mass of SiO, 0.5 parts by mass of acetylene black as a conductive additive, 1.8 parts by mass of sodium salt of carboxymethyl cellulose, and Example of binder composition 0.7 mass part is added as solid content of the binder composition E, water is further added so that solid content concentration of a slurry may be 50.5 mass%, and it mixes thoroughly using a planetary mixer, and obtains a slurry.
• An electrode was produced in the same manner as in Example 5-1 of the electrode except for the following. The thickness of the obtained electrode was 38 ⁇ m.
• the evaluation results of the adhesion test and the bending test are shown in Example 5-2 in Table 3.
• Example 1 of Table 2 As a electrolytic solution, a 1.4 mol / L tetraethylmethylammonium-tetrafluoroborate / propylene carbonate solution (manufactured by Kishida Chemical Co., Ltd.) was sufficiently impregnated and caulked, and a 2032 type coin battery for test was manufactured. The evaluation results of charge and discharge efficiency are shown in Example 1 of Table 2.
• Examplementation example 2 of coin battery (electrochemical capacitor)
• a coin battery was produced in the same manner as in Working Example 1 of a coin battery except that the positive electrode and the negative electrode obtained in Production Example 2 of the electrode were used.
• the evaluation results of charge and discharge efficiency are shown in Example 2 of Table 2.
• Example 3 of practical manufacture of coin battery (electrochemical capacitor)
• a coin battery was produced in the same manner as in Working Example 1 of a coin battery except that the positive electrode and the negative electrode obtained in Production Example 3 of the electrode were used.
• the evaluation results of charge and discharge efficiency are shown in Example 3 of Table 2.
• Example 4 of practical manufacture of coin battery (electrochemical capacitor)
• a coin battery was produced in the same manner as in Working Example 1 of a coin battery except that the positive electrode and the negative electrode obtained in Working Example 4 of the electrode were used.
• the evaluation results of charge and discharge efficiency are shown in Example 4 of Table 2.
• Examplementation example 5-2 of coin battery lithium ion battery
• Example of electrode A coin battery was manufactured in the same manner as Example of manufacturing coin cell 5-1 except that the negative electrode obtained in Example 5-2 was used.
• the evaluation results of the DC internal resistance and the charge and discharge efficiency are shown in Example 5-2 in Table 3.
• Table 2 shows the evaluation results of the physical properties of the activated carbon-containing electrodes of Examples and Comparative Examples, and the characteristic evaluation of the battery (electrochemical capacitor).
• the binder for an electrode of the present invention has excellent binding property to the activated carbon active material when used for an electrode, and also has excellent flexibility (flexibility). Moreover, while having excellent binding property also to a silicon compound, it is provided with excellent flexibility (flexibility), and since it is excellent in charge / discharge efficiency when it uses for an electrical storage device, an electric vehicle or a hybrid is obtained. It is usefully used in on-vehicle applications such as electric vehicles and storage devices such as storage batteries for household power storage.

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