WO2019017479A1 - Liant pour électrode, composition de liant pour électrode, matériau d'électrode, électrode et dispositif accumulateur de puissance - Google Patents

Liant pour électrode, composition de liant pour électrode, matériau d'électrode, électrode et dispositif accumulateur de puissance Download PDF

Info

Publication number
WO2019017479A1
WO2019017479A1 PCT/JP2018/027303 JP2018027303W WO2019017479A1 WO 2019017479 A1 WO2019017479 A1 WO 2019017479A1 JP 2018027303 W JP2018027303 W JP 2018027303W WO 2019017479 A1 WO2019017479 A1 WO 2019017479A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
mass
meth
structural unit
binder
Prior art date
Application number
PCT/JP2018/027303
Other languages
English (en)
Japanese (ja)
Inventor
一博 高橋
大明 進藤
義広 諸岡
松尾　孝
Original Assignee
株式会社大阪ソーダ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社大阪ソーダ filed Critical 株式会社大阪ソーダ
Priority to JP2019530618A priority Critical patent/JP7215420B2/ja
Priority to CN201880044362.7A priority patent/CN110832683B/zh
Publication of WO2019017479A1 publication Critical patent/WO2019017479A1/fr

Links

Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to storage devices such as primary batteries, secondary batteries such as lithium ion secondary batteries and nickel hydrogen secondary batteries, electrochemical capacitors, etc.
  • non-aqueous electrolyte storage batteries using non-aqueous electrolytes such as organic solvents as electrolytes.
  • the present invention relates to a binder for an electrode used in a device, a binder composition for an electrode including the binder for an electrode, an electrode material, 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.
  • This invention is made in view of the said situation, and it aims at providing the binder for electrodes which is excellent in the binding property at the time of using for an electrode.
  • a structural unit (A) derived from a monomer having a hydroxyl group represented by the following general formula (1) and an alkyl group having 4 to 6 carbon atoms A structural unit (B) derived from a (meth) acrylic acid ester monomer, having a structural unit (B-1) derived from a (meth) acrylic acid ester monomer containing a structural unit derived from a (meth) acrylic acid monomer
  • a polymer having 3.5 to 15% by mass of the structural unit (C) as a binder for an electrode, it is found that the polymer exhibits high binding property when used in an electrode, and the present invention is completed.
  • the present invention relates to the following.
  • R 1 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
  • n is an integer of 2 to 30.
  • the present invention relates to the following.
  • Item 1 The following general formula (1): (Wherein, R 1 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) Structural unit (A) derived from the monomer having a hydroxyl group represented by A structural unit (B) derived from a (meth) acrylic acid ester monomer, having a structural unit (B-1) derived from a (meth) acrylic acid ester monomer having an alkyl group having 4 to 6 carbon atoms; A structural unit (C) derived from a (meth) acrylic acid monomer, A structural unit (D) derived from a polyfunctional (meth) acrylate monomer having a functionality of 5 or less; Including A binder for an electrode, comprising: a polymer having 80 to 95% by mass of the structural unit (B) and 3.5 to 15% by mass of the structural unit (C).
  • Item 2 The binder for an electrode according to item 1, wherein in the general formula (1), n is an integer of 4 to 20.
  • Item 3 the pentafunctional or less polyfunctional (meth) acrylate monomer is represented by the following general formula (3): Wherein R 11 is the same or different and is a hydrogen atom or a methyl group, R 12 is a pentavalent or less organic group having 2 to 100 carbon atoms, and m is an integer of 5 or less. ) The binder for electrodes as described in 1 or 2 which is a compound shown by these. Item 4.
  • Item 5 The binder for an electrode according to any one of Items 1 to 4, which has 50 to 95% by mass of the structural unit (B-1).
  • Item 6. The binder for an electrode according to any one of Items 1 to 5, which has 0.5 to 15% by mass of the structural unit (A).
  • a binder composition for an electrode comprising the binder for an electrode according to any one of Items 1 to 7.
  • Item 9. An electrode material comprising the binder for an electrode according to any one of Items 1 to 7.
  • Item 10. An electrode comprising the binder for an electrode according to any one of Items 1 to 7 and an active material.
  • Item 11. Item 9. A storage device comprising the electrode according to item 8.
  • the binder for electrodes which is excellent in the binding property at the time of using for an electrode can be provided. Further, according to the present invention, it is possible to provide 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 exhibits excellent binding strength when used in a small battery (for example, a battery such as a mobile phone, a tablet terminal, a notebook computer, etc.) having a high density as compared with a large battery. can do.
  • a small battery for example, a battery such as a mobile phone, a tablet terminal, a notebook computer, etc.
  • the electrode using the binder for electrodes of this invention, and the electrical storage device provided with this electrode are especially useful to batteries, such as a mobile telephone, a tablet terminal, a notebook computer.
  • the power storage device includes a primary battery, a secondary battery (such as a lithium ion secondary battery and a nickel hydrogen secondary battery), and an electrochemical capacitor.
  • a secondary battery such as a lithium ion secondary battery and a nickel hydrogen secondary battery
  • an electrochemical capacitor such as a lithium ion secondary battery and a nickel hydrogen secondary battery
  • (meth) acrylate means “acrylate or methacrylate”, and the same applies to expressions similar thereto.
  • the binder for an electrode of the present invention is derived from a structural unit (A) derived from a monomer having a hydroxyl group represented by the following general formula (1) and a (meth) acrylic acid ester monomer having an alkyl group of 4 to 6 carbon atoms
  • Structural unit (B) derived from a (meth) acrylic acid ester monomer having a structural unit (B-1), a structural unit (C) derived from a (meth) acrylic acid monomer, and a pentafunctional or less polyfunctional functional group
  • R 1 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
  • n is an integer of 2 to 30.
  • the structural unit (A) is derived from the monomer having a hydroxyl group represented by the general formula (1).
  • R 1 is selected from a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • R 1 examples 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 1 is a hydrogen atom or a methyl group.
  • the monomer having a hydroxyl group is preferably a (meth) acrylate monomer (R 1 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 3 to 25, and more preferably an integer of 4 to 20.
  • the structural unit (A) is preferably derived from the monomer having a hydroxyl group represented by the general formula (2) below.
  • R 1 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms
  • o is an integer of 0 to 30
  • p is an integer of 0 to 30, and 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 1 examples 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 1 is a hydrogen atom or a methyl group.
  • the monomer having a hydroxyl group is preferably a (meth) acrylate monomer (R 1 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
  • o is an integer of 0 to 25 and p is 0 to 25
  • o is preferably an integer of 0 to 20
  • o is an integer of 0 to 20
  • p is an integer of 0 to 20
  • o + p is particularly preferably 4 to 20.
  • hydroxyl group-containing monomer represented by the general formula (1) 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 (A) may be of one type or of two or more types.
  • the lower limit of the ratio of the structural unit (A) is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, particularly preferably 2.5% by mass or more preferable.
  • the upper limit of the ratio of the structural unit (A) in the polymer is preferably 15% by mass or less, more preferably 12% by mass or less, and particularly preferably 10% by mass or less.
  • the structural unit (B) is a structural unit derived from a (meth) acrylic acid ester monomer.
  • the polymer has 80 to 95% by mass of the structural unit (B).
  • the structural unit (B) has a structural unit (B-1) derived from a (meth) acrylic acid ester monomer having an alkyl group of 4 to 6 carbon atoms.
  • the structural unit (B) may be composed of only the structural unit (B-1), and a structural unit (B-1) and a (meth) acrylic acid ester monomer having an alkyl group of 4 to 6 carbon atoms May have structural units (B-2) derived from different (meth) acrylic acid ester monomers.
  • the preferred structural unit (B-1) include n-butyl acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n- (meth) acrylate
  • Examples include structural units derived from (meth) acrylic acid alkyl esters such as hexyl and isohexyl (meth) acrylate, and n-butyl acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, It is more preferable that the structural unit is derived from a (meth) acrylic acid ester monomer having an alkyl group having 4 to 5 carbon atoms such as isopentyl (meth) acrylate.
  • the structural unit (B-1) of the structural unit (B) may be of one type or of two or more types.
  • the structural unit (B-2) contained in the structural unit (B) may be of one type or of two or more types.
  • the lower limit of the proportion of the structural unit (B) in the polymer is preferably 80% by mass or more, more preferably 82% by mass or more, and particularly preferably 84% by mass or more.
  • the upper limit of the ratio of the structural unit (B) in the polymer is preferably 95% by mass or less, more preferably 94% by mass or less, and particularly preferably 92% by mass or less.
  • the lower limit of the proportion of the structural unit (B-1) in the polymer is preferably 50% by mass or more, more preferably 65% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the proportion of the structural unit (B-1) in the polymer is preferably 95% by mass or less, more preferably 94% by mass or less, and particularly preferably 92% by mass or less.
  • the mass ratio of the structural unit (B-1) to the structural unit (A) is preferably 7: 1 to 35: 1, and more preferably 7.5 to 30: 1. Particularly preferred is 8: 1 to 25: 1.
  • the upper limit of the proportion of the structural unit (B-2) in the polymer is preferably 35% by mass or less, more preferably 23% by mass or less, and particularly preferably 10% by mass or less. Further, the lower limit of the proportion of the structural unit (B-2) in the polymer is 0% by mass or more, and may be 3% by mass or more, or 5% by mass or more.
  • the structural unit (C) is a structural unit derived from a (meth) acrylic acid monomer.
  • the polymer has 3.5 to 15% by mass of the structural unit (C).
  • the structural unit (C) of the polymer may be of one type or of two or more types.
  • the lower limit of the proportion of the structural unit (C) in the polymer is preferably 3.5% by mass or more, more preferably 4% by mass or more, and particularly preferably 5% by mass or more.
  • the upper limit of the proportion of the structural unit (C) is preferably 15% by mass or less, more preferably 13% by mass or less, and particularly preferably 12% by mass or less.
  • the structural unit (D) is a structural unit derived from a polyfunctional (meth) acrylate monomer having a functionality of five or less.
  • the structural unit (D) is preferably a structural unit derived from the following general formula (3).
  • R 11 is the same or different and is a hydrogen atom or a methyl group
  • R 12 is a pentavalent or less organic group having 2 to 100 carbon atoms
  • m is an integer of 5 or less It is.
  • m is preferably 2 to 5 (that is, a constituent unit derived from a difunctional to pentafunctional (meth) acrylate as the constituent unit (D)), and 3 to 5 (that is, a constituent 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-) Trifunctional (meth) acrylates such as (meth) acryloxyethyl) isocyanurate, glycerin EO-added tri (meth) acrylate, glycerol PO-added tri (meth) acrylate and tris (meth) acryloyloxyethyl phosphate Structural units and the like.
  • 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 lower limit of the ratio of the structural unit (D) in the polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more .
  • the upper limit of the proportion of the structural unit (D) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • the mass ratio of the structural unit (D) to the structural unit (A) in the polymer is preferably 0.03: 1 to 1.5: 1, and more preferably 0.05: 1 to 1: 1.
  • the ratio is preferably 0.08: 1 to 0.3: 1.
  • 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 Polymerization initiators of oil-soluble azo compounds such as carbonitriles) and redox initiators are preferred. 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 time and polymerization temperature of the polymer 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 polymer obtained by the above-mentioned method can be adjusted in pH by using a base as a pH adjuster as necessary.
  • 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.
  • 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 electrodes of the present invention may contain the aforementioned “1. binder for electrodes” together with a solvent, and the binder for electrodes may be dispersed in the solvent.
  • 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).
  • 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 active material, a negative electrode material used for the negative electrode
  • the binder for an electrode of the present invention may be contained, and further, a conductive auxiliary may be contained.
  • the positive electrode active material 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.
  • the cathode active material Li x CoO 2, Li x NiO 2, Li x MnO 2, Li x CrO 2, Li x FeO 2, Li x Co a Mn 1-a O 2, Li x Co a Ni 1-a O 2, Li x Co a Cr 1-a O 2, Li x Co a Fe 1-a O 2, Li x Co a Ti 1-a O 2, Li x Mn a Ni 1-a O 2 , Li x Mn a Cr 1 -a O 2 , Li x Mn a Fe 1 -a O 2 , Li x Mn a Ti 1 -a O 2 , Li x Ni a Cr 1 -a O 2 , Li x Ni a Fe 1-a O 2 , Li x Ni a Ti 1-a O 2 , Li x Cr a Fe 1-a O 2 , Li x Cr a Ti 1-a O 2 , Li x Fe a Ti 1-a O 2 , Li x Co b Mn c Ni 1-bc
  • the positive electrode active material include 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 x Mn f Fe 1 -f PO 4 can be mentioned.
  • a negative electrode active material a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (porous structure) capable of absorbing and desorbing lithium ions or lithium and aluminum-based materials capable of absorbing and desorbing lithium ions It is a powder made of a metal such as a compound, a tin-based compound, a silicon-based compound, and a titanium-based compound.
  • 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%.
  • 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, more preferably about 99.5 to 70% by mass, and still more preferably about 99 to 85% by mass.
  • Be 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 30 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 and titanium 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 pressing of the electrode is preferably performed so that the density of the electrode material is preferably 3.2 g / cc or more.
  • the binder for an electrode of the present invention is excellent in binding ability when used for a small battery (for example, a battery such as a mobile phone, a tablet terminal, a laptop computer) having a high density as compared with a large battery. Can be demonstrated. Therefore, in the electrode of the present invention, when the electrode material density has such a value, particularly excellent binding strength can be exhibited.
  • the upper limit of the density of the electrode material is generally 4.5 g / cc or less.
  • 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 tetraethylammonium tetrafluoroborate, triethylmonomethylammonium tetrafluoroborate, tetraethylammonium 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, if necessary, a separator or the like.
  • a positive electrode a negative electrode
  • an electrolytic solution if necessary, a separator or the like.
  • 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.
  • an electrode was manufactured, and a binding test of the electrode was performed in the following experiment as evaluation of the electrode.
  • 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 average particle size of the polymer was measured under the following conditions.
  • Particle size distribution measuring device using dynamic light scattering Zetasizer Nano (Spectris Co., Ltd.) (measurement conditions) 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 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 8.0 using a 28% aqueous ammonia solution, and a binder composition A (polymerization conversion rate 99% or more, solid content concentration 39.8 wt%) which is an emulsion solution Got). The average particle size of the obtained polymer was 0.273 ⁇ m. Polymer Synthesis The amounts of monomers used are shown in Table 1.
  • Examplementation Example 2 In a beaker, 72.34 parts by mass of n-butyl acrylate, 17.43 parts by mass of 2-ethylhexyl acrylate, 1.46 parts by mass of acrylic acid, 4.17 parts by mass of methacrylic acid, polyethylene glycol monomethacrylate (manufactured by NOF Corporation) : Brenmer PE-90 3.93 parts by mass, trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-TMPT) 0.67 parts by mass, 1 part by mass of sodium dodecyl sulfate as an emulsifier, 50.00 parts by mass of ion exchanged water And, 0.12 parts by mass of ammonium persulfate was added as a polymerization initiator, and the mixture was sufficiently stirred using an ultrasonic homogenizer to obtain an emulsion.
  • A-TMPT trimethylolpropane triacrylate
  • 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 2.6 to 8.0 using a 28% aqueous ammonia solution, and a binder composition B (polymerization conversion ratio of 99% or more, solid content concentration 40 wt%), which is an emulsion solution, Obtained. The average particle size of the obtained polymer was 0.237 ⁇ m. Polymer Synthesis The amounts of monomers used are 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 7.8 using a 28% aqueous ammonia solution, and an emulsion solution, binder composition C (polymerization conversion ratio 98% or more, solid content concentration 39 wt%) Obtained. The average particle size of the obtained polymer was 0.225 ⁇ m. Polymer Synthesis The amounts of monomers used are shown in Table 1.
  • Examplementation Example 4 In a beaker, 82.59 parts by mass of acrylic acid, 1.52 parts by mass of acrylic acid, 4.32 parts by mass of methacrylic acid, 10.88 parts by mass of polyethylene glycol monomethacrylate (manufactured by NOF Corporation: Blenmer PE-90) Part, 0.69 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical: A-TMPT), 1 part by mass of sodium dodecyl sulfate as an emulsifier, 50.00 parts by mass of ion exchanged water, and ammonium persulfate 0.12 as a polymerization initiator The parts by mass were added, and the mixture was sufficiently stirred using an ultrasonic homogenizer to give an emulsion.
  • 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 an emulsion solution, binder composition D (polymerization conversion ratio 98% or more, solid content concentration 39 wt%) Obtained. The average particle size of the obtained polymer was 0.230 ⁇ m.
  • 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 from 2.6 to 8.0 using a 28% aqueous ammonia solution, and a binder composition F (polymerization conversion rate: 99% or more, solid content concentration: 39 wt%) which is an emulsion solution Obtained. The average particle size of the obtained polymer was 0.205 ⁇ m.
  • Polymer Synthesis The amounts of monomers used are shown in Table 1.
  • Example 3 95 parts by mass of nickel.cobalt.manganate lithium as a positive electrode active material, 3 parts by mass of acetylene black as a conduction aid, 1 part by mass of carboxymethyl cellulose, and a binder composition. 1 part by mass was added as a portion, water was further added so that the solid content concentration of the slurry was 72% by mass, and sufficient mixing was performed using a planetary mill to obtain a slurry for a positive electrode.
  • the obtained positive electrode slurry is applied on a 20 ⁇ m thick aluminum current collector using a 100 ⁇ m gap Baker applicator, dried at 110 ° C. for 12 hours or more in a vacuum, and pressed using a roll press.
  • a positive electrode having a thickness of 36 ⁇ m and a density of 3.5 g / cc of the electrode material was produced.
  • the evaluation results of the binding test are shown in Example 1 of Table 1.
  • Example 4 of practical preparation of electrode Example 3 95 parts by mass of lithium cobalt cobalt lithium manganate as a positive electrode active material, 3 parts by mass of acetylene black as a conductive support agent, 1 part by mass of carboxymethyl cellulose, and a binder composition 1 part by mass is added as a portion, water is further added so that the solid content concentration of the slurry is 72% by mass, and sufficient mixing is performed using a planetary mill to obtain a slurry for positive electrode except that a slurry for positive electrode is obtained A positive electrode was produced in the same manner as in 1. The thickness of the obtained positive electrode was 41 ⁇ m, and the density of the electrode material was 3.2 g / cc. The evaluation results of the binding test are shown in Example 4 in Table 1.
  • Table 1 shows the evaluation results of the physical properties of the electrodes of the example and the comparative example.
  • the binder for electrodes of the present invention has excellent binding properties, and is usefully used in in-vehicle applications such as electric vehicles and hybrid electric vehicles, and storage devices such as storage batteries for household power storage.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un liant pour une électrode, qui présente d'excellentes propriétés liantes lorsqu'il est utilisé dans une électrode. Le liant pour une électrode comprend un polymère qui contient : des unités constitutives (A) dérivées d'un monomère contenant un groupe hydroxyle représenté par la formule générale (1) (dans la formule, R1 représente un atome d'hydrogène ou un groupe alkyle à chaîne droite ou ramifiée ayant entre 1 et 4 atomes de carbone, x est un entier compris entre 2 et 8, et n est un entier compris entre 2 et 30) ; des unités constitutives (B) dérivées d'un monomère d'ester d'acide (méth)acrylique, qui inclut des unités constituantes (B-1) dérivées d'un monomère d'ester d'acide (méth)acrylique ayant un groupe alkyle ayant entre 4 et 6 atomes de carbone ; des unités constitutives (C) dérivées d'un monomère d'acide (méth)acrylique ; et des unités constitutives (D) dérivées d'un monomère de (méth)acrylate pentafonctionnel ou polyfonctionnel inférieur. Le polymère contient entre 80 et 95 % en masse des unités constitutives (B) et entre 3,5 et 15 % en masse des unités constitutives (C).
PCT/JP2018/027303 2017-07-20 2018-07-20 Liant pour électrode, composition de liant pour électrode, matériau d'électrode, électrode et dispositif accumulateur de puissance WO2019017479A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019530618A JP7215420B2 (ja) 2017-07-20 2018-07-20 電極用バインダー、電極用バインダー組成物、電極材料、電極、及び蓄電デバイス
CN201880044362.7A CN110832683B (zh) 2017-07-20 2018-07-20 电极用粘结剂、电极用粘结剂组合物、电极材料、电极、以及蓄电装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017141020 2017-07-20
JP2017-141020 2017-07-20

Publications (1)

Publication Number Publication Date
WO2019017479A1 true WO2019017479A1 (fr) 2019-01-24

Family

ID=65016241

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/027303 WO2019017479A1 (fr) 2017-07-20 2018-07-20 Liant pour électrode, composition de liant pour électrode, matériau d'électrode, électrode et dispositif accumulateur de puissance

Country Status (3)

Country Link
JP (1) JP7215420B2 (fr)
CN (1) CN110832683B (fr)
WO (1) WO2019017479A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112467133B (zh) * 2020-03-30 2022-03-18 万向一二三股份公司 一种锂离子电池负极浆料及其制备方法
US20230114903A1 (en) * 2020-06-17 2023-04-13 Grst International Limited Binder composition for secondary battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017086215A1 (fr) * 2015-11-19 2017-05-26 旭化成株式会社 Liant pour dispositif de stockage d'électricité et composition de liant pour dispositif de stockage d'électricité
WO2017110901A1 (fr) * 2015-12-21 2017-06-29 株式会社大阪ソーダ Liant pour électrode de batterie, électrode, et batterie

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI489685B (zh) * 2009-08-07 2015-06-21 Jsr Corp Electrochemical devices and binder compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017086215A1 (fr) * 2015-11-19 2017-05-26 旭化成株式会社 Liant pour dispositif de stockage d'électricité et composition de liant pour dispositif de stockage d'électricité
WO2017110901A1 (fr) * 2015-12-21 2017-06-29 株式会社大阪ソーダ Liant pour électrode de batterie, électrode, et batterie

Also Published As

Publication number Publication date
JP7215420B2 (ja) 2023-01-31
CN110832683B (zh) 2023-03-14
JPWO2019017479A1 (ja) 2020-07-30
CN110832683A (zh) 2020-02-21

Similar Documents

Publication Publication Date Title
JP5447720B1 (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
JP6341271B2 (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
JP6269510B2 (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
WO2017110901A1 (fr) Liant pour électrode de batterie, électrode, et batterie
JP6164303B2 (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
JP6268988B2 (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
JP6300078B2 (ja) 電池電極用スラリー組成物、およびそれを用いた電極ならびに電池
WO2019131771A1 (fr) Liant pour électrodes, électrode et dispositif de stockage d'électricité
JP6395107B2 (ja) 電池電極用バインダー組成物、およびそれを用いた電極ならびに電池
WO2019017479A1 (fr) Liant pour électrode, composition de liant pour électrode, matériau d'électrode, électrode et dispositif accumulateur de puissance
JP2016046231A (ja) 電池正極用バインダー組成物、およびそれを用いた電極ならびに電池
CN110139881B (zh) 电极用粘结剂
JP2016192267A (ja) 電池電極用バインダー、およびそれを用いた電極ならびに電池
JP2019021575A (ja) 電極用バインダー、電極用バインダー組成物、電極材料、電極、及び蓄電デバイス
JP2018174044A (ja) 電極用バインダー、電極、及び蓄電デバイス
JP7088171B2 (ja) 電極用バインダー、電極材料、電極、及び蓄電デバイス
JP7180595B2 (ja) 電極及び蓄電デバイス
JP7314751B2 (ja) 水系バインダー組成物、電極、及び蓄電デバイス
JP2017091789A (ja) 正極、二次電池およびその製造方法
JP2017069006A (ja) 電池電極用バインダー組成物およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18835406

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019530618

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18835406

Country of ref document: EP

Kind code of ref document: A1