WO2014098233A1 - Matériau de résine de liaison destiné à des électrodes de dispositif énergétique, électrode de dispositif énergétique et dispositif énergétique - Google Patents

Matériau de résine de liaison destiné à des électrodes de dispositif énergétique, électrode de dispositif énergétique et dispositif énergétique Download PDF

Info

Publication number
WO2014098233A1
WO2014098233A1 PCT/JP2013/084317 JP2013084317W WO2014098233A1 WO 2014098233 A1 WO2014098233 A1 WO 2014098233A1 JP 2013084317 W JP2013084317 W JP 2013084317W WO 2014098233 A1 WO2014098233 A1 WO 2014098233A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
energy device
group
electrode
Prior art date
Application number
PCT/JP2013/084317
Other languages
English (en)
Japanese (ja)
Inventor
正嗣 青谷
祐一 利光
鈴木　健司
Original Assignee
日立化成株式会社
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 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2014553228A priority Critical patent/JPWO2014098233A1/ja
Publication of WO2014098233A1 publication Critical patent/WO2014098233A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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 relates to a binder resin material for an energy device electrode, an energy device electrode, and an energy device.
  • Lithium ion secondary batteries which are energy devices with high energy density, are widely used as power sources for portable information terminals such as notebook computers, mobile phones and PDAs.
  • this lithium ion secondary battery (hereinafter, also simply referred to as “lithium battery”), carbon having a multilayer structure capable of inserting and releasing lithium ions between layers (formation of a lithium intercalation compound) and release as an active material of a negative electrode Material is mainly used.
  • lithium-containing metal composite oxide is mainly used as the positive electrode active material.
  • An electrode of a lithium battery is usually prepared by kneading these active materials, a binder resin material and a solvent (N-methyl-2-pyrrolidone, water, etc.) to prepare an electrode mixture slurry.
  • a metal foil as a current collector is applied to one or both sides of a current collector with a transfer roll or the like, the solvent is removed to form a mixture layer, and then compression molded with a roll press or the like.
  • properties required for the binder resin material include adhesion between the active materials and between the active material and the current collector, swelling resistance to the electrolytic solution, electrochemical stability, flexibility, and electrode composition using the same. And the viscosity stability of the agent slurry. Furthermore, in order to increase the capacity of the lithium battery, it is required to sufficiently satisfy these characteristics even when the amount of the binder resin material added is small. However, the conventional binder resin material does not sufficiently satisfy these characteristics.
  • a modified poly (meth) acrylonitrile binder obtained by copolymerizing a short-chain monomer such as a 1-olefin having 2 to 4 carbon atoms and / or an alkyl (meth) acrylate having 3 or less carbon atoms
  • a binder resin material obtained by blending a resin and a rubber component having a glass transition temperature of ⁇ 80 ° C. to 0 ° C. is disclosed (for example, see Japanese Patent No. 4300239).
  • the solvent used for preparing the electrode mixture slurry it is preferable to use water from the viewpoint of reducing the environmental load.
  • water When water is used as a solvent, a method of dispersing a binder resin material with water is known.
  • a thickener such as carboxymethyl cellulose in combination.
  • a problem may occur in the adhesion, the stability of the electrode mixture slurry, and the like.
  • metal-based negative electrode materials have been proposed as high-capacity negative electrode active materials.
  • the metal-based negative electrode material has a high capacity, but has a large volume expansion / contraction due to charge / discharge. Therefore, in the binder resin material used conventionally, the adhesiveness of the interface between the mixture layer and the current collector and the adhesiveness between the active materials in the mixture layer are insufficient, and it is remarkable by repeating the charge / discharge cycle. The problem is that the capacity decreases. Therefore, a binder resin material having excellent adhesion that can be used in the metal-based negative electrode material as described above is required. In this regard, it has been proposed to use lithium polyacrylate as a binder for a tin-cobalt-carbon composite composite negative electrode (see, for example, Electrochimica Acta., 55 (2010), 2991-2995).
  • Poly (meth) acrylonitrile is excellent in adhesion between active materials and between active materials and current collectors, but electrode mixture slurries using the same tend to easily increase in viscosity over time, and may have poor storage stability. there were.
  • poly (meth) acrylonitrile tends to have a low elastic modulus in the high temperature rubber region, and the charge / discharge cycle characteristics at high temperatures are not always satisfactory.
  • An object of the present invention is to provide a binder resin material for an energy device electrode capable of preparing an electrode mixture slurry excellent in storage stability and capable of forming an energy device electrode excellent in adhesion between the mixture layer and a current collector. There is to do. Moreover, the objective of this invention is comprised using the binder resin material for energy device electrodes, and is providing the energy device electrode which is excellent in the adhesiveness of a mixture layer and a collector. Furthermore, the objective of this invention is providing the energy device by which the capacity
  • a binder resin material for an energy device electrode containing a copolymer containing a structural unit derived from (meth) acrylonitrile and a structural unit derived from a compound having two or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is the binder resin material for an energy device electrode according to ⁇ 1>, which is a compound represented by the following general formula (I).
  • each R 1 independently represents a hydrogen atom or a methyl group.
  • R 2 represents an n-valent organic group.
  • N represents a number of 2 to 6.
  • a copolymer comprising a current collector and a structural unit derived from (meth) acrylonitrile and a compound having two or more ethylenically unsaturated bonds, provided on at least one surface of the current collector , As well as a mixture layer containing an active material.
  • An energy device comprising the energy device electrode according to ⁇ 4>, a counter electrode of the energy device electrode, and an electrolyte.
  • the energy device according to ⁇ 5> which is a lithium ion secondary battery.
  • the binder resin material for energy device electrodes which can form the energy device electrode which can prepare the electrode mixture slurry excellent in storage stability, and is excellent in the adhesiveness of a mixture layer and a collector is provided. can do. Moreover, it is comprised using the binder resin material for energy device electrodes, and the energy device electrode which is excellent in the adhesiveness of a mixture layer and a collector can be provided. Furthermore, the energy device in which the capacity
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .
  • (Meth) acrylate means at least one of acrylate and the corresponding methacrylate
  • (meth) acrylic acid means at least one of acrylic acid and methacrylic acid
  • (meth) allyl means allyl and methallyl
  • (meth) acrylonitrile means at least one of acrylonitrile and methacrylonitrile.
  • the term “monomer” means a polymerizable compound having only one ethylenically unsaturated bond, and a crosslinkable polymerizable compound having two or more ethylenically unsaturated bonds; Means something different.
  • the binder resin material for energy device electrodes of the present invention comprises a copolymer (hereinafter referred to as “specific copolymer”) containing a structural unit derived from (meth) acrylonitrile and a structural unit derived from a compound having two or more ethylenically unsaturated bonds. At least one kind of "combined”.
  • the energy device electrode binder resin material may contain other components such as a solvent and a surfactant, as necessary.
  • an electrode mixture slurry is constituted by having a specific copolymer having a structural unit derived from a compound having two or more ethylenically unsaturated bonds in addition to a structural unit derived from (meth) acrylonitrile, Increase in viscosity is suppressed and storage stability is excellent. Moreover, when the energy device electrode is configured using the binder resin material for the energy device electrode, the adhesion between the mixture layer and the current collector is excellent.
  • the specific copolymer Since the specific copolymer has a cross-linked structural unit in addition to the highly polar structural unit, when the electrode mixture slurry is composed using this, the increase in viscosity over time is suppressed and stored. It is considered excellent in stability.
  • the specific copolymer has a highly polar structural unit and the energy device electrode is configured using the binder resin material for the energy device electrode containing the specific copolymer, the adhesion between the mixture layer and the current collector It is considered excellent.
  • the storage elastic modulus in the high-temperature rubber region is increased because the specific copolymer has a structure in which highly polar structural units are crosslinked. Thereby, it is thought that an energy device provided with the energy device electrode which has the mixture layer containing a specific copolymer is excellent in especially the charge / discharge cycle characteristic in high temperature.
  • the electrode produced using the binder resin material for the energy device electrode has excellent adhesion between the mixture layer and the current collector, so that the electrode mixture slurry is applied to the current collector and dried. It is possible to suppress the peeling of the mixture layer from the current collector during winding in the pressed state, during slit processing, during pressing, and after pressing. Furthermore, the binder resin material for energy device electrodes of the present invention, as described above, can be used even in a small amount because a mixture layer with excellent adhesion to the current collector can be obtained, and the amount of binder resin material used Can be reduced.
  • An energy device (preferably a lithium battery) including an electrode manufactured using the binder resin material for an energy device electrode has good conductivity because it easily follows expansion and contraction due to charging / discharging of an active material. The capacity reduction in the discharge cycle is suppressed.
  • the specific copolymer includes a structural unit derived from a monomer (meth) acrylonitrile and a structural unit derived from a compound having two or more ethylenically unsaturated bonds (hereinafter also referred to as “crosslinking agent”). .
  • the said specific copolymer may further contain the structural unit derived from other monomers other than (meth) acrylonitrile as needed.
  • the specific copolymer is a monomer composition containing (meth) acrylonitrile, other monomers used as necessary, and a compound (crosslinking agent) having two or more ethylenically unsaturated bonds. It can be obtained by polymerization.
  • One type of monomer constituting each structural unit may be selected and used for polymerization in each structural unit, or a plurality of types may be selected and used for polymerization. Further, one type of monomer may be selected as a monomer constituting a specific structural unit, and a plurality of types of monomers may be selected as monomers constituting other structural units.
  • the specific copolymer should just contain each structural unit mentioned above, and there is no restriction
  • the specific copolymer may be either a block copolymer or a random copolymer, and is preferably a random copolymer.
  • the specific copolymer includes a structural unit derived from (meth) acrylonitrile. That is, the specific copolymer includes a structural unit derived from at least one selected from the group consisting of acrylonitrile and methacrylonitrile.
  • the structural unit derived from (meth) acrylonitrile is preferably a structural unit derived from acrylonitrile from the viewpoint of flexibility and the like.
  • the content of the structural unit derived from (meth) acrylonitrile in the specific copolymer is not particularly limited.
  • the content of structural units derived from (meth) acrylonitrile is based on the total number of structural units derived from the monomer of the specific copolymer from the viewpoint of excellent adhesion between the current collector and the mixture layer in the energy device electrode. (100 mol%) is preferably 20 mol% to 70 mol%, and more preferably 30 mol% to 60 mol% from the viewpoint of excellent adhesion and storage stability of the electrode mixture slurry. More preferably, it is 35 mol% to 45 mol%.
  • the compound having two or more ethylenically unsaturated bonds includes two or more functional groups containing an ethylenically unsaturated bond and an organic group that is a divalent or higher linking group that links the functional groups to each other. If it is a compound which has this, there will be no restriction
  • the compound having two or more ethylenically unsaturated bonds is preferably, for example, a compound represented by the following general formula (I).
  • R ⁇ 1 > shows a hydrogen atom or a methyl group each independently.
  • R 2 represents an n-valent organic group.
  • n represents a number of 2 to 6 and is preferably 3 to 4.
  • n is an integer when the compound represented by formula (I) is a single molecular species.
  • the n-valent organic group represented by R 2 is an n-valent aliphatic hydrocarbon having 2 to 20 carbon atoms formed by removing n hydrogen atoms from an aliphatic hydrocarbon having 2 to 20 carbon atoms.
  • R 2 is an n-valent aliphatic hydrocarbon group having 2 to 11 carbon atoms formed by removing n hydrogen atoms from an aliphatic hydrocarbon having 2 to 11 carbon atoms and 3 to 3 carbon atoms. It is preferably at least one selected from the group consisting of n-valent organic groups formed by removing n hydroxy groups from 11 polyhydric alcohols or hydroxyalkylated products thereof, and aliphatic groups having 3 to 11 carbon atoms A trivalent to tetravalent aliphatic hydrocarbon group having 3 to 11 carbon atoms and a polyhydric alcohol having 3 to 11 carbon atoms or a hydroxyalkyl thereof having 3 to 11 carbon atoms formed by removing 3 to 4 hydrogen atoms from the hydrocarbon More preferably, it is at least one selected from the group consisting of trivalent to tetravalent organic groups formed by removing 3 to 4 hydroxy groups from the compound.
  • Specific examples of compounds having two or more ethylenically unsaturated bonds include 1,4-butanediol diacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-124AS), nonanediol diacrylate (Hitachi Chemical Co., Ltd.).
  • the compound having two or more ethylenically unsaturated bonds is preferably a trifunctional or tetrafunctional acrylate having 3 or 4 (meth) acrylic groups, and has a carbon number of 3 to 11
  • a poly (meth) acrylic acid ester of a monohydric alcohol is more preferable, and pentaerythritol triacrylate or ethoxylated pentaerythritol tetraacrylate is more preferable.
  • These compounds having two or more ethylenically unsaturated bonds can be used singly or in combination of two or more.
  • the content of the structural unit derived from the compound having two or more ethylenically unsaturated bonds in the specific copolymer is not particularly limited.
  • the content of the structural unit derived from a compound having two or more ethylenically unsaturated bonds increases the storage elastic modulus in the rubber-like region of the specific copolymer, and follows the expansion and contraction of the active material during charging and discharging of the energy device. From the viewpoint of facilitating the treatment, it is preferably 0.01 to 5.0 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass of the total monomer-derived mass in the specific copolymer.
  • the amount is more preferably 0 part by mass, and further preferably 0.02 part by mass to 2.0 parts by mass.
  • the content rate of the structural unit derived from the compound having two or more ethylenically unsaturated bonds in the specific copolymer is specified in mol%, the total number of structural units derived from the monomer in the specific copolymer (100 mol) %) To 0.001 mol% to 1.0 mol%, more preferably 0.005 mol% to 0.5 mol%, and 0.02 mol% to 0.2 mol%. More preferably, it is mol%.
  • the molar ratio of the content of the structural unit derived from the compound having two or more ethylenically unsaturated bonds to the content of the structural unit derived from (meth) acrylonitrile in the specific polymer is not particularly limited. From the viewpoint of excellent adhesion between the current collector and the mixture layer in the energy device electrode, the molar ratio is preferably 0.008 mol% to 0.8 mol%, preferably 0.03 mol% to 0.00. More preferably, it is 3 mol%.
  • the specific copolymer may further include at least one structural unit derived from a monomer other than the structural unit derived from (meth) acrylonitrile, if necessary.
  • the other monomer include a monomer represented by the following general formula (II), a monomer represented by the following general formula (III), and an acidic functional group-containing monomer.
  • R 21 represents a hydrogen atom or a methyl group.
  • R 22 represents a 2-cyanoethyl group, an alkyl group having 3 to 20 carbon atoms, or a hydroxyalkyl group having 5 to 20 carbon atoms.
  • the alkyl group having 3 to 20 carbon atoms for R 22 may be a branched alkyl group or a linear alkyl group, and is preferably a linear alkyl group.
  • the number of carbon atoms in the alkyl group represented by R 22 is preferably 3 to 12, and more preferably 3 to 8.
  • alkyl group having 3 to 20 carbon atoms represented by R 22 include propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, and 1,1-dimethylethyl.
  • the alkyl group represented by R 22 is a propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl, which is an alkyl group having 3 to 12 carbon atoms.
  • the alkyl group constituting the hydroxyalkyl group having 5 to 20 carbon atoms in R 22 may be a branched alkyl group or a linear alkyl group, and is preferably a linear alkyl group. .
  • the number of carbon atoms of the hydroxyalkyl group represented by R 22 is preferably 5 to 12, and more preferably 5 to 8.
  • hydroxyalkyl group having 5 to 20 carbon atoms represented by R 22 include 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, and 9-hydroxynonyl.
  • the hydroxyalkyl group represented by R 22 is a 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, which is a hydroxyalkyl group having 5 to 12 carbon atoms, 8
  • a 5-hydroxyoctyl group, a 9-hydroxynonyl group, a 10-hydroxydecyl group, an 11-hydroxyundecyl group, or a 12-hydroxydodecyl group is preferable, and 5-hydroxy which is a hydroxyalkyl group having 5 to 8 carbon atoms.
  • a pentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, or 8-hydroxyoctyl group is more preferable.
  • the monomer represented by the general formula (II) include 2-cyanoethyl (meth) acrylate, propyl (meth) acrylate, 1-methylethyl (meth) acrylate, butyl (meth) acrylate, and 1-methyl.
  • the monomers represented by the general formula (II) are propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) from the viewpoint of ease of synthesis.
  • R 31 represents a hydrogen atom or a methyl group.
  • X represents an alkylene group having 2 to 4 carbon atoms.
  • m represents a number from 1 to 10.
  • R 32 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • X is preferably an alkylene group having 2 or 3 carbon atoms.
  • m is preferably a number from 1 to 6, more preferably from 1 to 4.
  • m is an integer when the compound represented by the general formula (III) is a single molecular species, and is a rational number that is an average value when including a plurality of molecular species.
  • the alkyl group represented by R 32 may be a branched alkyl group or a linear alkyl group, and is preferably a linear alkyl group.
  • the alkyl group represented by R 32 preferably has 1 to 3 carbon atoms.
  • alkyl group having 1 to 5 carbon atoms represented by R 32 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, 1 , 1-dimethylethyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1 -An ethylpropyl group and the like can be mentioned.
  • the alkyl group represented by R 32 is preferably a methyl group, an ethyl group, or a propyl group from the viewpoint of ease of synthesis and the like.
  • monomer represented by the general formula (III) examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and diethylene glycol mono (meth).
  • Acrylate triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, heptaethylene glycol mono (meth) acrylate, octaethylene glycol Alkylene glycol mono (meth) acrylates such as mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, decaethylene glycol mono (meth) acrylate; Tyl monoethylene glycol (meth) acrylate, methyldiethylene glycol (meth) acrylate, methyltriethylene glycol (meth) acrylate, methyltetraethylene glycol (meth) acrylate, methylpentaethylene glycol (meth) acrylate, methylhexaethylene glycol (meth) Acrylate, methylheptaethylene glycol (meth) acrylate, methyl octaethylene
  • the monomer represented by the general formula (III) includes 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, methyl monoethylene glycol (meth) Acrylate, methyldiethylene glycol (meth) acrylate, methyltriethylene glycol (meth) acrylate, methyltetraethylene glycol (meth) acrylate, methylpentaethylene glycol (me Acrylate), methyl hexaethylene glycol (meth) acrylate, ethyl monoethylene glycol (meth) acrylate, ethyl diethylene glycol (meth) acrylate, ethyl
  • the specific copolymer is a monomer represented by the structural unit derived from the monomer represented by the general formula (II) and the monomer represented by the general formula (III) from the viewpoint of adjusting the glass transition temperature (Tg) described later. It is preferable to further include at least one structural unit selected from the group consisting of derived structural units.
  • the specific copolymer includes 1 structural unit selected from the group consisting of a structural unit derived from the monomer represented by the general formula (II) and a structural unit derived from the monomer represented by the general formula (III).
  • One species may be included alone, or two or more species may be combined and included.
  • the specific copolymer includes at least one structural unit derived from a monomer represented by the general formula (II) and a structural unit derived from the monomer represented by the general formula (III)
  • the contents of the structural unit derived from the monomer represented by the general formula (II) and the structural unit derived from the monomer represented by the general formula (III) are not particularly limited, and are appropriately selected according to the purpose and the like. be able to.
  • the total content of the structural unit derived from the monomer represented by the general formula (II) and the structural unit derived from the monomer represented by the general formula (III) is the current collector and the mixture layer in the energy device electrode.
  • the resin is preferably 30 to 80 mol% based on the total amount of structural units derived from monomers in the specific copolymer (100 mol%). From the viewpoint of excellent storage stability of the mixture slurry, it is more preferably 40 mol% to 70 mol%, and further preferably 55 mol% to 65 mol%.
  • the specific copolymer includes both a structural unit derived from the monomer represented by the general formula (II) and a structural unit derived from the monomer represented by the general formula (III), the general formula (II).
  • the content ratio of the structural unit derived from the monomer represented by) and the structural unit derived from the monomer represented by the general formula (III) is not particularly limited, and the monomer represented by the general formula (II) And can be appropriately selected according to the structure of the monomer represented by formula (III).
  • the specific copolymer includes a structural unit derived from the monomer represented by the general formula (II), among the monomers represented by the general formula (II), R 22 represents a 2-cyanoethyl group.
  • the content of the monomer-derived structural unit is 5 on the basis of the total structural unit amount derived from the monomer in the specific copolymer (100 mol%). It is preferably at most mol%, more preferably substantially at 0 mol%, still more preferably at 0 mol%.
  • the acidic functional group-containing monomer is not particularly limited as long as it is a compound having an acidic functional group and a functional group containing an ethylenically unsaturated bond.
  • the acidic functional group include a carboxy group, a sulfo group, a phosphoric acid group, a phenolic hydroxyl group, and salts thereof.
  • acidic functional group-containing monomers examples include carboxylic group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, citraconic acid, vinyl benzoic acid, and carboxyethyl acrylate; Sulfo group-containing monomers such as acid, sodium (meth) allylsulfonate, sodium (meth) allyloxybenzenesulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid; acid phosphoxyethyl methacrylate ( Unichemical Co., Ltd., trade name: Phosmer M), acid phosphoxypolyoxyethylene glycol monomethacrylate (Unichemical Co., Ltd., trade name: Phosmer PE), 3-chloro-2-acid phosphoxypropyl methacrylate Phosphoric acid group-containing monomers such as Todo (Unichemical Co., Ltd., trade name: Phosphor
  • At least one selected from the group consisting of acrylic acid, methacrylic acid, and 2-carboxyethyl acrylate is preferable from the viewpoints of ease of synthesis, adhesion between active materials, and the like.
  • These acidic functional group-containing monomers can be used alone or in combination of two or more.
  • the content is not particularly limited.
  • the content of the structural unit derived from the acidic functional group-containing monomer can be, for example, 0.01 mol to 10 mol with respect to 1 mol of the structural unit derived from (meth) acrylonitrile. If the content of the structural unit derived from the acidic functional group-containing monomer is 0.01 mol or more, the effect of improving the adhesion between the active materials and between the mixture layer and the current collector is sufficient in the specific copolymer. Demonstrated.
  • the content rate of the structural unit derived from an acidic functional group-containing monomer is 10 mol or less, the structural unit derived from the above-mentioned (meth) acrylonitrile-derived structural unit and a compound having two or more ethylenically unsaturated bonds The characteristics derived from are sufficiently exhibited in the specific copolymer.
  • the specific copolymer is derived from a monomer represented by the general formula (II) or a structural unit derived from the monomer represented by the general formula (III) as a structural unit derived from another monomer.
  • a structural unit derived from a monomer other than the structural unit derived from the structural unit and the acidic functional group-containing monomer may further be included.
  • short chain (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate
  • Vinyl halides such as acrylic ester, vinyl chloride, vinyl bromide, vinylidene chloride, maleic imide, phenylmaleimide, (meth) acrylamide, styrene, ⁇ -methylstyrene, vinyl acetate, 1,1-bis (trifluoromethyl) ) -2,2,2-trifluoroethyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, Nonafluoroisobutyl acrylate, 2,2,3,3,4,4,5,5-octafluoro Pentyl
  • the content is not particularly limited.
  • the content of structural units derived from other monomers can be, for example, 0.01 to 10 moles per mole of structural units derived from (meth) acrylonitrile.
  • the content of the structural unit derived from another monomer is 0.01 mol or more, the characteristics derived from the other monomer are sufficiently exhibited in the specific copolymer.
  • the content rate of the structural unit derived from another monomer is 10 mol or less, it is derived from the structural unit derived from the above-mentioned (meth) acrylonitrile-derived structural unit and a compound having two or more ethylenically unsaturated bonds. This characteristic is sufficiently exhibited in the specific copolymer.
  • the glass transition temperature (Tg) of the specific copolymer is not particularly limited.
  • the glass transition temperature of the specific copolymer is preferably 25 ° C. to 120 ° C., which is higher than the storage temperature of the electrode mixture slurry and lower than the drying temperature at the time of producing the energy device electrode, and is 30 ° C. to 80 ° C. More preferably, it is more preferably 35 ° C. to 50 ° C. If the glass transition temperature is 25 ° C. or higher, the electrode mixture slurry tends to be more excellent in storage stability. Moreover, if the glass transition temperature is 120 ° C. or lower, the adhesiveness of the energy device electrode tends to be better.
  • the glass transition temperature of the specific copolymer can be measured under normal measurement conditions by dynamic viscoelasticity measurement (DMA).
  • DMA dynamic viscoelasticity measurement
  • the storage elastic modulus of the specific copolymer is not particularly limited and can be appropriately selected according to the purpose.
  • the storage elastic modulus of the specific copolymer is preferably 1.0 MPa to 60 MPa, more preferably 1.1 MPa to 50 MPa at 60 ° C. from the viewpoint of cycle characteristics at a high temperature of the energy device.
  • the storage elastic modulus of the specific copolymer can be measured by forming the specific copolymer into a film and measuring the dynamic viscoelasticity (DMA).
  • the specific copolymer is a monomer (meth) acrylonitrile from the viewpoint of the storage stability of the electrode mixture slurry, the adhesion between the mixture layer and the current collector in the energy device electrode, and the adhesion between the active materials.
  • the second structural unit derived from the compound (crosslinking agent) represented by the general formula (I) is added in an amount of 0.001 mol% to 1. mol based on 100 mol% of the total number of structural units derived from the monomer. An embodiment containing 0 mol% is preferable.
  • the first structural unit is contained in an amount of 30 mol% to 60 mol%
  • the third structural unit is contained in an amount of 40 mol% to 70 mol%
  • the second structural unit is derived from a monomer.
  • the structural unit is contained in an amount of 0.005 mol% to 0.5 mol% with respect to the total number of structural units of 100 mol%.
  • the first structural unit is contained in an amount of 30 mol% to 60 mol%
  • the third structural unit is contained in an amount of 40 mol% to 70 mol%
  • the second structural unit is derived from a monomer.
  • the structural unit is contained in an amount of 0.005 mol% to 0.5 mol% with respect to the total number of structural units of 100 mol%, and the glass transition temperature is 25 ° C. to 120 ° C.
  • the specific copolymer in the present invention includes (meth) acrylonitrile, a compound having two or more ethylenically unsaturated bonds, and, if necessary, a monomer represented by the general formula (II), a general formula ( It is produced by polymerizing a monomer composition constituted by appropriately combining the monomer represented by III), an acidic functional group-containing monomer, and other monomers other than these monomers. be able to.
  • the polymerization mode for producing the specific copolymer in the present invention is not particularly limited, and examples thereof include precipitation polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Precipitation polymerization or emulsion polymerization is preferable in terms of ease of copolymer synthesis, ease of post-treatment such as recovery and purification.
  • a polymerization initiator for the polymerization of the monomer composition.
  • a water-soluble polymerization initiator is preferable in view of polymerization initiation efficiency and the like.
  • Water-soluble polymerization initiators include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; water-soluble peroxides such as hydrogen peroxide; 2,2′-azobis (2-methylpropionamidine hydrochloride) Water-soluble azo compounds such as persulfates; reducing agents such as sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, and hydrosulfite; and polymerization accelerators such as sulfuric acid, iron sulfate, and copper sulfate.
  • Redox type (redox type) etc. which used together.
  • persulfate or a water-soluble azo compound is preferable from the viewpoint of ease of copolymer synthesis.
  • Water-soluble means that the solubility in 100 g of pure water at 25 ° C. is 1 g or more.
  • the polymerization initiator is preferably used in the range of 0.001 mol% to 5 mol% with respect to the total amount (100 mol%) of monomers used in the specific copolymer, from the viewpoint of polymerization efficiency. Is more preferably used in the range of 0.01 mol% to 2 mol%.
  • a chain transfer agent can be used as necessary for the purpose of adjusting the molecular weight.
  • the chain transfer agent include mercaptan compounds, thioglycol, carbon tetrachloride, ⁇ -methylstyrene dimer and the like. Of these, ⁇ -methylstyrene dimer is preferred from the viewpoint of low odor.
  • the chain transfer agent is preferably used in the range of 0.001% by mass to 3% by mass with respect to the total amount (100% by mass) of monomers used in the specific copolymer, from the viewpoint of molecular weight control. More preferably, it is used in the range of 0.01% by mass to 3% by mass. When the amount of the chain transfer agent used is in the range of 0.001% to 3% by mass, it can be easily controlled to a desired molecular weight, which is preferable.
  • surfactants When polymerizing the monomer composition to obtain a specific copolymer, various surfactants can be used as necessary. There is no restriction
  • anionic surfactant examples include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfates such as sodium lauryl sulfate; polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene polycyclic phenyl ether Oxyethylene alkyl ether sulfates; fatty acid salts such as sodium stearate soap; cellulose derivatives such as carboxymethylcellulose; and the like.
  • alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate
  • alkyl sulfates such as sodium lauryl sulfate
  • polyoxyethylene lauryl ether sodium sulfate polyoxyethylene polycyclic phenyl ether Oxyethylene alkyl ether sulfates
  • fatty acid salts such as sodium stearate soap
  • cellulose derivatives such as carboxymethylcellulose; and the like.
  • Nonionic surfactants include polyoxyethylene polycyclic phenyl ethers such as polyoxyethylene biphenyl ether; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyalkylene derivatives such as polyoxyalkylene alkyl ethers.
  • Sorbitan fatty acid esters such as sorbitan monolaurate; glycerin fatty acid esters such as glycerol monostearate; polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate; cellulose derivatives such as methylcellulose, ethylcellulose, and hydroxypropylcellulose; .
  • examples of the cationic surfactant include alkylamine salts such as stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride; and the like.
  • an anionic surfactant or a nonionic surfactant is preferable, and an anionic interface is preferable.
  • An activator is more preferred.
  • carboxymethylcellulose having an anionic surfactant which is frequently used as a thickener in the electrode mixture slurry preparation step in the production of energy device electrodes, which will be described in detail later, has battery characteristics. It is more preferable because it does not have an adverse effect.
  • the surfactant can be used alone or in combination of two or more.
  • the surfactant is preferably used in the range of 0.001% by mass to 5% by mass with respect to the total amount (100% by mass) of monomers used in the specific copolymer, and 0.01% by mass. More preferably, it is used in the range of ⁇ 1% by mass.
  • the amount of the surfactant used is in the range of 0.001% by mass to 5% by mass, the particle diameter can be easily controlled, and aggregation during polymer synthesis can be suppressed, which is preferable.
  • the solvent for synthesizing the specific copolymer by a polymerization reaction includes water, but depending on the purpose such as adjustment of the precipitated particle diameter and improvement of wettability when performing precipitation polymerization and emulsion polymerization or after completion of the polymerization.
  • a solvent other than water can also be added.
  • solvents other than water examples include amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide; N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea, tetra Urea solvents such as methyl urea; lactone solvents such as ⁇ -butyrolactone and ⁇ -caprolactone; carbonate solvents such as propylene carbonate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; methyl acetate, ethyl acetate, n-butyl acetate , Ester solvents such as butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate and ethyl carbitol acetate; glyme solvents such as diglyme,
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of solvent used is not particularly limited.
  • the amount of the solvent used is preferably in the range of 50% by mass to 2000% by mass, and in the range of 100% by mass to 1000% by mass, based on the total amount of monomers used in the specific copolymer. More preferably.
  • the monomer composition is introduced into a solvent further containing a polymerization initiator, if necessary, and the polymerization temperature is 0 ° C. to 100 ° C., preferably 40 ° C. to 90 ° C.
  • the polymerization time is carried out by maintaining the polymerization time at a predetermined temperature for 1 hour to 50 hours, preferably 2 hours to 12 hours. If the polymerization temperature is 0 ° C. or higher, the polymerization proceeds efficiently, and if the polymerization temperature is 100 ° C. or lower, even when water is used as a solvent, water is prevented from completely evaporating. Polymerization can be performed efficiently.
  • (meth) acrylonitrile, acidic functional group-containing monomers and the like have a large polymerization heat, so the monomer composition is appropriately dropped in a solvent. However, it is preferable to proceed the polymerization.
  • the polymerization mode is precipitation polymerization
  • water, alcohol, hexane, ethyl acetate, toluene or the like is preferable to use water, alcohol, hexane, ethyl acetate, toluene or the like as a solvent.
  • the polymerization temperature is preferably 40 ° C. to 100 ° C.
  • the polymerization time is preferably 2 hours to 8 hours.
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition is preferably 40% by mass to 70% by mass.
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition is preferably 40% by mass to 70% by mass.
  • the polymerization rate is not too high, the structural unit derived from the crosslinking agent is sufficiently introduced, and the storage elastic modulus in the rubber-like region of the film made of only the binder resin material for energy device electrodes is improved.
  • the reaction conversion rate of the monomer is 40% or more, a sufficient reaction rate is obtained and the polymerization reaction tends to proceed efficiently.
  • the dropping time of the monomer composition is 1 hour to 3 hours
  • the reaction conversion rate of the monomer after dropping the monomer composition is 40 mass% to 70 mass%
  • the total polymerization It is preferable to proceed the polymerization reaction while appropriately controlling the polymerization temperature in accordance with the synthesis scale or the like so that the time is 2 to 8 hours.
  • a surfactant from the viewpoint of dispersion stability of the monomer and the copolymer to be produced, ease of control of the particle size of the copolymer, and the like.
  • the details of the surfactant are as described above.
  • the pH of the copolymer dispersion obtained by emulsion polymerization is preferably 3 to 10, more preferably 5 to 8, and still more preferably 6 to 8 close to neutrality.
  • the pH is 3 or more, substitution of hydrogen atoms with the sodium salt of carboxymethylcellulose, a thickener that may be used when producing energy device electrodes, is suppressed, and the electrode mixture slurry due to a decrease in water solubility There is a tendency that the increase in the viscosity of the resin and the precipitation or aggregation of carboxymethylcellulose are suppressed.
  • the pH is 10 or less, hydrolysis of the thickener is suppressed, and the storage stability of the electrode mixture slurry tends to be improved.
  • the specific copolymer is used as a binder resin material for energy device electrodes. That is, another aspect of the present invention is the use of a copolymer containing a structural unit derived from (meth) acrylonitrile and a structural unit derived from a compound having two or more ethylenically unsaturated bonds in a binder resin material for an energy device electrode. It is.
  • the binder resin material for an energy device electrode may further contain other components such as a solvent and a surfactant, if necessary, in addition to at least one of the specific copolymers. That is, one aspect of the binder resin material for energy device electrodes is a dispersion in which the specific copolymer is dispersed in a solvent.
  • solvent As a suitable solvent for dispersing the specific copolymer, water is preferable. Further, in addition to water, solvents other than water such as the alcohol solvent described above, hydrocarbon solvents such as hexane and toluene, and ester solvents such as ethyl acetate can be used in combination.
  • the binder resin material for energy device electrodes of the present invention can be used in a form in which the solvent used when the specific copolymer is produced is removed and dispersed or dissolved in a desired solvent.
  • Suitable solvents for dispersing or dissolving the specific copolymer include amide solvents, urea solvents, lactone solvents, and mixed solvents thereof.
  • amide solvents such as N-methyl-2-pyrrolidone, lactone solvents such as ⁇ -butyrolactone, or mixed solvents thereof are more preferable from the viewpoint of dispersion or solubility. These solvents are used singly or in combination of two or more.
  • the amount of the solvent used is not particularly limited as long as it is more than the necessary minimum amount capable of maintaining the dispersed or dissolved state of the specific copolymer at room temperature, and is usually an electrode mixture slurry preparation step in the subsequent production of the energy device electrode. In order to adjust the viscosity while adding a solvent, it is preferable to use an arbitrary amount that is not excessively diluted.
  • the amount of the solvent used is preferably an amount such that the solid content concentration of the specific copolymer in the binder resin material for energy device electrodes is 5% by mass to 60% by mass, and an amount that provides 10% by mass to 50% by mass. It is more preferable that
  • the specific copolymer when the specific copolymer is obtained in a state where the specific copolymer is dispersed in a solvent, the dispersion of the specific copolymer obtained according to the method for manufacturing the specific copolymer is used as it is. It is also possible to use it as a binder resin material for an energy device electrode of the present invention.
  • the binder resin material for energy device electrodes may further contain a surfactant, a thickener, other additives, etc., if necessary.
  • an anionic surfactant As the surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, or a combination thereof can be used. Specific examples of the anionic surfactant, the nonionic surfactant and the cationic surfactant are as described above.
  • the surfactants include alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyethylene lauryl ether.
  • Polyoxyethylene alkyl ether sulfate such as sodium sulfate and polyoxyethylene polycyclic phenyl ether; Polyoxyalkylene derivatives such as polyoxyethylene alkyl ether; Sorbitan fatty acid ester; Glycerin fatty acid ester; Polyoxyethylene fatty acid ester; Carboxymethyl cellulose, Methyl cellulose Celluloses such as ethyl cellulose, hydroxypropyl cellulose, and ammonium salts or alkali metal salts thereof; polyacrylic acid and alkalis thereof Preferred is a genus salt; an ethylene-methacrylic acid copolymer; a polyvinyl alcohol copolymer such as polyvinyl alcohol and an ethylene-vinyl alcohol copolymer; and the like, celluloses such as carboxymethyl cellulose, and ammonium salts or alkali metal salts thereof. More preferred.
  • the ratio of the surfactant in the binder resin material for energy device electrodes of the present invention is not particularly limited, and from the viewpoint of dispersion stability, the surfactant is 0.0001 parts by mass to 0 parts by mass with respect to 1 part by mass of the specific copolymer. 0.1 part by mass is preferable, 0.0001 part by mass to 0.05 part by mass is more preferable, and 0.0001 part by mass to 0.01 part by mass is still more preferable.
  • the binder resin material for energy device electrodes further contains at least one thickener. Thereby, in the electrode mixture slurry preparation process in preparation of the energy device electrode explained in full detail later, it can adjust to desired viscosity easily.
  • the thickener examples include celluloses such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and ammonium salts or alkali metal salts thereof; polyacrylic acid and alkali metal salts thereof; ethylene-methacrylic acid copolymer; polyvinyl alcohol And polyvinyl alcohol polymers such as ethylene-vinyl alcohol copolymer.
  • the adhesive is preferably 0.1 to 3 parts by mass, more preferably 0.3 to 2 parts by mass, and further preferably 0.5 to 1.5 parts by mass. preferable.
  • the binder resin material for the energy device electrode is a material other than the above as necessary, a conductive aid for complementing the conductivity of the electrode, a rubber component for complementing the flexibility or flexibility of the electrode, Various additives such as an anti-settling agent, an antifoaming agent and a leveling agent for further improving the electrode coatability of the electrode mixture slurry can also be contained.
  • a non-aqueous electrolyte-type energy device refers to an electricity storage or power generation device (apparatus) that uses an electrolyte containing an organic solvent other than water.
  • Examples of the non-aqueous electrolyte energy device include a lithium battery, an electric double layer capacitor, and a solar battery.
  • the binder resin material for energy device electrodes has high resistance to swelling with respect to a non-aqueous electrolyte containing an organic solvent other than water when the energy device electrode is formed, it is preferably used particularly in the formation of electrodes for lithium batteries. .
  • the binder resin material for the energy device electrode is not only the energy device electrode, but also the paint, adhesive, curing agent, printing ink, solder resist, abrasive, electronic component sealing material, semiconductor surface protective film or interlayer insulation. It can be widely used for various coating resins such as membranes, varnishes for electrical insulation and biomaterials, molding materials and fibers.
  • an energy device electrode and an energy device using the electrode will be described.
  • the energy device electrode of the present invention has a current collector and a mixture layer provided on at least one surface of the current collector.
  • the mixture layer includes a copolymer (specific copolymer) including a structural unit derived from a compound having an active material and (meth) acrylonitrile and a compound having two or more ethylenically unsaturated bonds.
  • the mixture layer contains the specific copolymer, the adhesion between the mixture layer and the current collector is excellent.
  • the energy device comprised using the said energy device electrode suppresses the capacity
  • the current collector may be any material having conductivity, and for example, a metal can be used.
  • the material and shape of the current collector are not particularly limited. Examples of the material of the current collector include aluminum, copper, nickel, titanium, stainless steel, porous metal (foamed metal), and carbon paper. Examples of the shape of the current collector include a foil shape, a perforated foil shape, and a mesh shape. From the viewpoint of increasing the energy density of the energy device, a thin film is preferable.
  • the thickness of the current collector is, for example, 5 ⁇ m to 30 ⁇ m, preferably 8 ⁇ m to 25 ⁇ m.
  • the mixture layer contains at least one active material and at least one specific copolymer, and may contain other components as necessary. Details of the specific copolymer are as described above.
  • the active material is not particularly limited, and is appropriately selected according to the configuration of the energy device.
  • the active material include those capable of reversibly inserting and releasing lithium ions by charging and discharging the lithium battery.
  • the active material used by a positive electrode and a negative electrode normally uses a different material according to each function.
  • the positive electrode has a function of releasing lithium ions during charging and receiving lithium ions during discharging, while the negative electrode receives lithium ions during charging and releases lithium ions during discharging. Therefore, the active materials used for the positive electrode and the negative electrode are usually made of different materials in accordance with the respective functions.
  • carbon materials such as graphite, amorphous carbon, carbon fiber, coke and activated carbon are preferable.
  • a composite of such a carbon material and a metal such as silicon, tin, silver, or an oxide thereof can be preferably used. These negative electrode active materials are used alone or in combination of two or more.
  • the positive electrode active material is not particularly limited, and a metal compound, metal oxide, metal sulfide, conductive polymer material, or the like that can be doped or intercalated with lithium ions may be used.
  • the positive electrode active material is preferably a lithium-containing metal composite oxide containing lithium and at least one metal selected from iron, cobalt, nickel, and manganese.
  • the lithium-containing metal composite oxide lithium manganese composite oxide, lithium cobalt composite oxide, lithium nickel composite oxide, or the like is used.
  • These lithium-containing metal composite oxides further include at least one metal selected from Al, V, Cr, Fe, Co, Sr, Mo, W, Mn, B, and Mg, and include lithium sites, manganese, and cobalt.
  • a lithium-containing metal composite in which sites such as nickel are substituted can be used.
  • an active material is 40 mass parts with respect to 1 mass part of specific copolymers. Is preferably from 130 parts by weight, more preferably from 80 parts by weight to 120 parts by weight, and still more preferably from 90 parts by weight to 110 parts by weight.
  • Each of these active materials may be used in combination with a conductive additive.
  • the conductive assistant include graphite, carbon black, and acetylene black. These conductive aids may be used alone or in combination of two or more.
  • the content of the conductive assistant in the mixture layer is preferably 0.001 to 0.1 parts by mass, and 0.01 to 0.1 parts by mass with respect to 1 part by mass of the active material. More preferably, the content is 0.01 parts by mass to 0.05 parts by mass.
  • the energy device electrode is used for at least one of a positive electrode and a negative electrode of the energy device.
  • the energy device electrode is preferably used as a negative electrode of the energy device.
  • the energy device electrode can be manufactured using a known electrode manufacturing method without any particular limitation. For example, an electrode mixture slurry containing a binder resin material for an energy device electrode containing the specific copolymer, a solvent, an active material, etc. is applied to at least one surface of the current collector, and then at least a part of the solvent is removed. If necessary, it can be further rolled to form a mixture layer on the current collector surface.
  • the mixture layer is prepared, for example, by kneading the binder resin material for an energy device electrode, an active material, and the like together with a solvent by a dispersing device such as a stirrer, a ball mill, a super sand mill, and a pressure kneader to prepare an electrode mixture slurry.
  • a dispersing device such as a stirrer, a ball mill, a super sand mill, and a pressure kneader to prepare an electrode mixture slurry.
  • this electrode mixture slurry is applied to the current collector, and the solvent is removed by drying.
  • the solvent used for forming the mixture layer is not particularly limited as long as it can dissolve or disperse the binder resin material for energy device electrodes.
  • water is preferable.
  • various solvents such as an organic solvent can be used.
  • the organic solvent include amide solvents such as N-methyl-2-pyrrolidone and lactone solvents such as ⁇ -butyrolactone. These solvents may be used alone or in combination of two or more.
  • the viscosity of the electrode mixture slurry to be adjusted in the slurry preparation step is 500 mPa ⁇ s to 50000 mPa ⁇ s at 25 ° C. when 10% by mass of the specific copolymer is dispersed or dissolved in the total amount of the electrode mixture slurry. It is preferably s, more preferably 1000 mPa ⁇ s to 20000 mPa ⁇ s, and still more preferably 2000 mPa ⁇ s to 10000 mPa ⁇ s.
  • the electrode mixture slurry to the current collector can be performed, for example, by a coating method.
  • the coating method is not particularly limited, and may be appropriately selected from known coating methods.
  • the coating method can be performed using a comma coater or the like.
  • the coating is suitably performed so that the active material utilization rate per unit area is equal to or greater than negative electrode / positive electrode between the opposing electrodes.
  • the application amount of the electrode mixture slurry is, for example, such that the dry mass of the mixture layer is 10 g / m 2 to 150 g / m 2 , preferably 40 g / m 2 to 110 g / m 2 .
  • the removal of the solvent is carried out by drying at 50 ° C. to 150 ° C., preferably 80 ° C. to 120 ° C. for 1 minute to 20 minutes, preferably 3 minutes to 10 minutes.
  • the rolling process is performed using, for example, a roll press.
  • the mixture layer is pressed so that the bulk density of the mixture layer is, for example, 1 g / cm 3 to 2 g / cm 3 , preferably 1.2 g / cm 3 to 1.8 g / cm 3 .
  • the mixture layer is pressed so that the bulk density of the mixture layer is, for example, 2 g / cm 3 to 5 g / cm 3 , and preferably 3 g / cm 3 to 4 g / cm 3 .
  • vacuum drying may be performed at 100 to 150 ° C. for 1 to 20 hours.
  • the energy device of the present invention includes the energy device electrode of the present invention, an electrode serving as a counter electrode of the energy device electrode, and an electrolyte.
  • the energy device may have other components as necessary. Since the energy device of the present invention has a highly adherent and highly elastic energy device electrode, the capacity drop in the charge / discharge cycle is small.
  • the energy device examples include a lithium battery, an electric double layer capacitor, a hybrid capacitor, and a solar battery. Among them, at least one selected from the group consisting of an electric double layer capacitor, a hybrid capacitor, and a lithium battery is preferable. Is more preferable.
  • an energy device will be described by taking a lithium battery as an example. The details of the energy device electrode in the lithium battery are as described above.
  • Electrode as a counter electrode for the energy device electrode When the energy device electrode of the present invention constitutes a negative electrode, the electrode serving as the counter electrode of the energy device electrode constitutes a positive electrode. On the other hand, when the energy device electrode of the present invention constitutes a positive electrode, the electrode serving as the counter electrode of the energy device electrode constitutes a negative electrode.
  • the electrode which becomes a counter electrode of an energy device electrode is not specifically limited, According to an energy device electrode, it can select from a well-known electrode suitably and can be used.
  • the electrolyte is not particularly limited as long as it functions as a lithium battery that is an energy device, for example.
  • As the electrolyte LiClO 4, LiBF 4, LiI , LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, Li [(C 2 O 4 ) 2 B] and the like.
  • LiPF 6 , LiBF 4 And at least one selected from the group consisting of Li (CF 3 SO 2 ) 2 N is preferred, and LiPF 6 or LiBF 4 is more preferred.
  • the electrolyte is preferably used as an electrolytic solution dissolved in a solvent other than water.
  • Solvents other than water include carbonate solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactone solvents such as ⁇ -butyrolactone; trimethoxymethane, 1,2-dimethoxyethane, diethyl Ether solvents such as ether, 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxide solvents such as dimethyl sulfoxide; oxolane solvents such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; acetonitrile, nitromethane, N -Nitrogen-containing solvents such as methyl-2-pyrrolidone; ester solvents such as methyl formate, methyl acetate,
  • an electrolytic solution obtained by dissolving LiPF 6 in carbonate solvents are preferred.
  • the electrolytic solution is prepared by using, for example, the above organic solvent and an electrolyte alone or in combination of two or more. Further, the electrolytic solution may contain 0.1% by mass to 3.0% by mass of vinylene carbonate or the like as a Solid Electrolyte Interface (SEI) layer forming agent as necessary.
  • SEI Solid Electrolyte Interface
  • Inject the electrolyte into the obtained battery can, weld the tab terminal that was previously welded to the positive electrode current collector to the battery lid, and place the lid on the top of the battery can via the insulating gasket
  • the lithium battery can be obtained by caulking and sealing the portion where the lid and the battery can are in contact.
  • the form of the lithium ion secondary battery is not particularly limited, and examples thereof include lithium ion secondary batteries such as paper batteries, button batteries, coin batteries, stacked batteries, cylindrical batteries, and prismatic batteries.
  • Example 1 In a 0.5 liter three-necked flask equipped with a stirrer, thermometer, condenser, and liquid feed pump, 335 g of water and 2% aqueous solution of carboxymethyl cellulose (manufactured by Daicel Finechem, trade name: CMC # 2200) as an emulsifier 21.46 g was added, and after the pressure was reduced to 2.6 kPa (20 mmHg) with an aspirator, the operation of returning to normal pressure with nitrogen was repeated three times to remove dissolved oxygen. The flask was maintained in a nitrogen atmosphere, heated to 60 ° C.
  • carboxymethyl cellulose manufactured by Daicel Finechem, trade name: CMC # 2200
  • Emulsion polymerization is carried out by dropping with a liquid pump over 2 hours. .
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition was 51%.
  • the temperature was raised to 80 ° C., and stirring was further continued for 2 hours to obtain a binder resin material for an energy device electrode as an aqueous dispersion of the specific copolymer.
  • About 1 ml of the obtained aqueous dispersion was weighed in an aluminum pan, dried on a hot plate heated to 160 ° C. for 15 minutes, and the non-volatile content was calculated from the weight of the residue to find 15.3% (copolymer yield 98 %)Met.
  • Example 2 168 g of water, carboxymethylcellulose (manufactured by Daicel Finechem, trade name: CMC # 2200) 2% aqueous solution 10.79 g, potassium persulfate 0.13 g, acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 19.84 g (total amount) Butyl methacrylate (ratio of 40 mol% in the body mass (100 mol%)), a monomer represented by the general formula (II) (R 21 is a methyl group, R 22 is a butyl group having 4 carbon atoms) Wako Pure Chemical Industries, Ltd.) 79.76 g (60 mol% in total monomer amount (100 mol%)), compound represented by general formula (I) (R 1 is hydrogen atom, n Is ethoxylated pentaerythritol tetraacrylate (trade name: ATM-4E, manufactured by Shin-Nakamura Chemical Co., Ltd.) where
  • Example 2 Example 2 % was carried out in the same manner as in Example 1 except that 0.1 mol%) was used to obtain a binder resin material for energy device electrodes.
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition was 59%.
  • About 1 ml of the aqueous dispersion was weighed into an aluminum pan, dried on a hot plate heated to 160 ° C. for 15 minutes, and the non-volatile content was calculated from the residue weight. As a result, it was 13.9% (copolymer yield 99%). there were.
  • Example 3 Water 201 g, Carboxymethylcellulose (Daicel Finechem, trade name: CMC # 2200) 2% aqueous solution 12.89 g, Potassium persulfate 0.16 g, Acrylonitrile (Wako Pure Chemical Industries, Ltd.) 20.66 g (total amount) Butyl acrylate (a proportion of 40 mol% in the body weight (100 mol%)), a monomer represented by the general formula (II) (R 21 is a hydrogen atom, R 22 is a butyl group having 4 carbon atoms) 37.42 g (manufactured by Wako Pure Chemical Industries, Ltd.) (a proportion of 30 mol% in the total monomer amount (100 mol%)), a monomer represented by the general formula (II) (R 21 is a methyl group) , R 22 is a butyl methacrylate having 4 carbon atoms) 41.51 g (manufactured by Wako Pure Chemical Industries, Ltd
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition was 51%.
  • About 1 ml of the aqueous dispersion was weighed into an aluminum pan, dried on a hot plate heated to 160 ° C. for 15 minutes, and the nonvolatile content was calculated from the weight of the residue. As a result, 16.7% (99% yield of copolymer) was obtained. there were.
  • Example 4 199 g of water, carboxymethyl cellulose (manufactured by Daicel Finechem, trade name: CMC # 2200) 2% aqueous solution 13.53 g, potassium persulfate 0.16 g, acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 20.30 g (total amount) Butyl acrylate (a proportion of 41 mol% in the body weight (100 mol%)) and a monomer represented by the general formula (II) (R 21 is a hydrogen atom, R 22 is a butyl group having 4 carbon atoms) Wako Pure Chemical Industries, Ltd.) 47.63 g (40 mol% in total monomer amount (100 mol%)), monomer represented by general formula (II) (R 21 is hydrogen atom) , R 22 is a 2-ethylhexyl group having 8 carbon atoms) 31.83 g (manufactured by Wako Pure Chemical Industries, Ltd.)
  • a binder resin material for an energy device electrode was obtained in the same manner as in Example 1 except that 24 g (ratio of 0.06 mol% with respect to the total monomer amount (100 mol%)) was used.
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition was 55%.
  • About 1 ml of the aqueous dispersion was weighed into an aluminum pan, dried on a hot plate heated to 160 ° C. for 15 minutes, and the non-volatile content was calculated from the residue weight. As a result, it was 17.8% (copolymer yield 97%). there were.
  • ⁇ Comparative Example 1 Operation of adding 274 g of water into a 0.5 liter four-necked flask equipped with a stirrer, thermometer, condenser, and liquid feed pump, reducing the pressure to 2.6 kPa (20 mmHg) with an aspirator, and then returning to atmospheric pressure with nitrogen was repeated three times to remove dissolved oxygen.
  • the flask was kept in a nitrogen atmosphere and heated to 65 ° C. with stirring in an oil bath, and then 0.13 g of potassium persulfate was dissolved in 4 g of water and added to the four-necked flask.
  • 2-cyanoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a monomer represented by the general formula (II) (R 21 is a hydrogen atom, R 22 is a 2-cyanoethyl group) ) 26.69 g (a proportion of 30 mol% in the total monomer amount (100 mol%)), a monomer represented by the general formula (II) (R 21 is a hydrogen atom, R 22 is a carbon number of 4 Butyl acrylate (produced by Wako Pure Chemical Industries, Ltd.) 43.81 g (a proportion of 48 mol% in the total monomer amount (100 mol%)), which is represented by the general formula (II) 29.28 g of 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) (R 21 is hydrogen and R 22 is a 2-ethylhexyl group having 8 carbon atoms)
  • the reaction conversion rate of the monomer after completion of dropping of the monomer composition was 73%.
  • the temperature was raised to 80 ° C., and stirring was further continued for 2 hours to obtain a binder resin material for an energy device electrode as an aqueous dispersion of a copolymer.
  • About 1 ml of the aqueous dispersion was weighed into an aluminum pan, dried on a hot plate heated to 160 ° C. for 15 minutes, and the non-volatile content was calculated from the residue weight. As a result, it was 19.2% (copolymer yield 96%). there were.
  • ⁇ Comparative Example 2> In a 0.3 liter four-necked flask equipped with a stirrer, thermometer, condenser, and feed pump, 201 g of water and polyoxyethylene polycyclic phenyl ether as an emulsifier (trade name: New, manufactured by Nippon Emulsifier Co., Ltd.) The operation of adding 0.89 g of a 30% aqueous solution of Cole 707SF), reducing the pressure to 2.6 kPa (20 mmHg) with an aspirator, and then returning to normal pressure with nitrogen was repeated three times to remove dissolved oxygen. The inside of the flask was kept in a nitrogen atmosphere, heated to 65 ° C.
  • Example 5 Graphite negative electrode material (trade name: MAG, manufactured by Hitachi Chemical Co., Ltd.) 98 parts by mass, binder resin material for energy device electrode obtained in Example 1 (non-volatile content: 15.3% by mass) 6.5 parts by mass ( 1 mass part in terms of non-volatile content), carboxymethylcellulose (manufactured by Daicel Finechem, trade name: CMC # 2200) 66.7 parts by mass (non-volatile content 1.5 mass%) in water (non-volatile content 1 mass part) are mixed, Further, water was added to adjust the viscosity to prepare an electrode mixture slurry (non-volatile content: 48% by mass).
  • binder resin material for energy device electrode obtained in Example 1 6.5 parts by mass ( 1 mass part in terms of non-volatile content), carboxymethylcellulose (manufactured by Daicel Finechem, trade name: CMC # 2200) 66.7 parts by mass (non-volatile content 1.5 mass%) in water (non-vola
  • Example 6> This was performed in the same manner as in Example 5 except that 7.2 parts by mass (1 part by mass of non-volatile content) of the binder resin material for energy device electrodes (non-volatile content of 13.9% by mass) obtained in Example 2 was used. .
  • Example 7 It carried out like Example 5 except having used 6.0 mass parts (nonvolatile content conversion 1 mass part) binder resin material for energy device electrodes obtained in Example 3 (nonvolatile content 16.7 mass%). .
  • Example 8 It carried out like Example 5 except having used 5.6 mass parts (nonvolatile matter conversion 1 mass part) binder resin material for energy device electrodes (nonvolatile matter 17.8 mass%) obtained in Example 4. .
  • Viscosity measurement conditions The viscosity measurement conditions and the electrode mixture slurry storage conditions are shown below.
  • Measuring instrument VISCONIC E [manufactured by Tokimec] Sample volume: 1 ml Rotational speed: 10 rpm (shear speed: 38.3 s ⁇ 1 ) Measurement temperature: 25 ° C (Storage conditions) Storage: Rotary mixer 40 rpm stirring Storage temperature: 25 ° C
  • glass transition temperature (Tg) of the obtained copolymer was measured using the above DMA measuring device RSA-III [manufactured by TA instruments]. The measurement results are shown in Table 2.
  • the electrode mixture slurries of Examples 5 to 8 produced using the specific copolymers obtained in Examples 1 to 4 were produced using the copolymers obtained in Comparative Examples 1 and 2. It can be seen that the storage stability of the electrode mixture slurry is superior to the electrode mixture slurry of Comparative Examples 3 and 4. That is, the specific copolymer (Examples 1 to 4) can satisfy excellent storage stability when applied to the energy device electrode mixture slurry.
  • Example 9 Obtained in Example 5 electrode mixture slurry rolled copper foil (current collector, thickness 10 [mu] m) to the mass of the dried mixture layer 99g / m 2 ⁇ 101g / m 2 to become like coating machine The gap was adjusted and uniformly coated, and then dried for 1 hour with a blow-type dryer set at 105 ° C., and further for 5 hours at 120 ° C. to produce a sheet-like energy device electrode for negative electrode.
  • Example 10 The same operation as in Example 9 was carried out except that the electrode mixture slurry obtained in Example 6 was used.
  • Example 11 The same operation as in Example 9 was carried out except that the electrode mixture slurry obtained in Example 7 was used.
  • Example 12 The same operation as in Example 9 was performed except that the electrode mixture slurry obtained in Example 8 was used.
  • ⁇ Production of lithium battery> 88 parts by mass of a positive electrode active material (LiCoO 2 ) and 6 parts by mass of a conductive additive (HS-100), 25 parts by mass of a binder resin (PVDF (polyvinylidene fluoride), 12% by mass, NMP (N-methylpyrrolidone) solution
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the application amount of the electrode mixture layer (not including the current collector) to the current collector (aluminum foil, thickness 21 ⁇ m) is 220 g / m 2 to 226 g. / G 2 after adjusting the gap of the coating machine to be uniform and then drying with a blow-type dryer set at 100 ° C. for 1 hour and further at 120 ° C. for 1 hour, for a sheet-like positive electrode An energy device electrode was fabricated.
  • Example 13 The energy device electrode for negative electrode produced in Example 9 was compression-molded with a roll press machine so that the bulk density of the mixture layer was 1.5 mg / cm 3, and then cut into a 1.6 cm diameter circle for evaluation. An electrode was obtained.
  • the adhesion between the mixture layer and the current collector in the energy device electrodes of Examples 9 to 12 produced using the specific copolymers obtained in Examples 1 to 4 is a comparative example. It turns out that it is superior to the energy device electrodes of 5 and 6. It can also be seen that the specific copolymers (Examples 1 to 4) exhibit a high elastic modulus at 60 ° C., which is not obtained in Comparative Examples (7, 8). Furthermore, the 60 ° C. cycle characteristics of the lithium batteries (Examples 13 to 16) produced using the binder resin material for energy device electrodes of the present invention were superior to those of Comparative Examples (Comparative Examples 7 and 8).
  • a binder resin material for an energy device electrode capable of forming an electrode mixture slurry excellent in storage stability and an energy device electrode excellent in adhesion between the current collector and the mixture layer, and the use thereof Energy device electrodes and long life energy devices can be provided.

Abstract

La présente invention concerne un matériau de résine de liaison destiné à des électrodes de dispositif énergétique, lequel contient un copolymère qui comprend un motif structurel dérivé de (méth)acrylonitrile et un motif structurel dérivé d'un composé possédant deux liaisons à insaturation éthylénique ou plus.
PCT/JP2013/084317 2012-12-20 2013-12-20 Matériau de résine de liaison destiné à des électrodes de dispositif énergétique, électrode de dispositif énergétique et dispositif énergétique WO2014098233A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014553228A JPWO2014098233A1 (ja) 2012-12-20 2013-12-20 エネルギーデバイス電極用バインダ樹脂材料、エネルギーデバイス電極及びエネルギーデバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012278434 2012-12-20
JP2012-278434 2012-12-20

Publications (1)

Publication Number Publication Date
WO2014098233A1 true WO2014098233A1 (fr) 2014-06-26

Family

ID=50978547

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/084317 WO2014098233A1 (fr) 2012-12-20 2013-12-20 Matériau de résine de liaison destiné à des électrodes de dispositif énergétique, électrode de dispositif énergétique et dispositif énergétique

Country Status (3)

Country Link
JP (1) JPWO2014098233A1 (fr)
TW (1) TWI637551B (fr)
WO (1) WO2014098233A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016031837A (ja) * 2014-07-29 2016-03-07 株式会社大阪ソーダ 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
WO2016152056A1 (fr) * 2015-03-24 2016-09-29 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
CN111226328A (zh) * 2017-10-27 2020-06-02 日本瑞翁株式会社 蓄电装置用粘接剂组合物、蓄电装置用功能层、蓄电装置及蓄电装置的制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132893A (ja) * 2001-10-26 2003-05-09 Nippon Zeon Co Ltd 電極用スラリー組成物、電極およびリチウムイオン二次電池
JP2003223895A (ja) * 2002-01-31 2003-08-08 Nippon Zeon Co Ltd 二次電池電極用スラリー組成物、二次電池電極および二次電池
JP2006040800A (ja) * 2004-07-29 2006-02-09 Hitachi Chem Co Ltd リチウム電池電極用バインダ樹脂溶液及びこの溶液と活物質から製造される電極および電池
JP2011014409A (ja) * 2009-07-02 2011-01-20 Nippon Zeon Co Ltd リチウムイオン二次電池用電極の製造方法及び複合粒子
JP2012204303A (ja) * 2011-03-28 2012-10-22 Nippon Zeon Co Ltd 二次電池用電極、二次電池電極用バインダー、製造方法及び二次電池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112005001483B4 (de) * 2004-06-21 2017-03-23 Sekisui Chemical Co., Ltd. Bindemittelharz-Zusammensetzung, und deren Verwendung als Paste und Grünfolie
JPWO2008029502A1 (ja) * 2006-08-29 2010-01-21 ユニチカ株式会社 電極形成用バインダー、そのバインダーを用いた電極形成用スラリー、そのスラリーを用いた電極、その電極を用いた二次電池、その電極を用いたキャパシタ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132893A (ja) * 2001-10-26 2003-05-09 Nippon Zeon Co Ltd 電極用スラリー組成物、電極およびリチウムイオン二次電池
JP2003223895A (ja) * 2002-01-31 2003-08-08 Nippon Zeon Co Ltd 二次電池電極用スラリー組成物、二次電池電極および二次電池
JP2006040800A (ja) * 2004-07-29 2006-02-09 Hitachi Chem Co Ltd リチウム電池電極用バインダ樹脂溶液及びこの溶液と活物質から製造される電極および電池
JP2011014409A (ja) * 2009-07-02 2011-01-20 Nippon Zeon Co Ltd リチウムイオン二次電池用電極の製造方法及び複合粒子
JP2012204303A (ja) * 2011-03-28 2012-10-22 Nippon Zeon Co Ltd 二次電池用電極、二次電池電極用バインダー、製造方法及び二次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016031837A (ja) * 2014-07-29 2016-03-07 株式会社大阪ソーダ 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
WO2016152056A1 (fr) * 2015-03-24 2016-09-29 三洋電機株式会社 Batterie rechargeable à électrolyte non aqueux
JPWO2016152056A1 (ja) * 2015-03-24 2018-01-11 三洋電機株式会社 非水電解質二次電池
CN111226328A (zh) * 2017-10-27 2020-06-02 日本瑞翁株式会社 蓄电装置用粘接剂组合物、蓄电装置用功能层、蓄电装置及蓄电装置的制造方法

Also Published As

Publication number Publication date
TWI637551B (zh) 2018-10-01
TW201429034A (zh) 2014-07-16
JPWO2014098233A1 (ja) 2017-01-12

Similar Documents

Publication Publication Date Title
CN107710471B (zh) 二次电池电极用粘结剂组合物、二次电池电极用浆料组合物、二次电池用电极及二次电池
WO2015146649A1 (fr) Suspension pour électrode positive d'accumulateur électrique au lithium-ion, électrode positive obtenue en utilisant ladite suspension, procédé de fabrication de ladite électrode positive, accumulateur électrique au lithium-ion formé en utilisant ladite électrode positive, et procédé de fabrication dudit accumulateur
KR20190085918A (ko) 전기 화학 소자용 바인더
JP5790193B2 (ja) エネルギーデバイス電極用バインダ樹脂材料、エネルギーデバイス電極及びエネルギーデバイス
WO2018168520A1 (fr) Composition de liant pour batteries à électrolyte non aqueux, et solution aqueuse de liant pour batteries à électrolyte non aqueux, composition de suspension pour batteries à électrolyte non aqueux, électrode pour batteries à électrolyte non aqueux et batterie à électrolyte non aqueux utilisant chacune ladite composition de liant
JP6789498B2 (ja) エネルギーデバイス電極形成用組成物、エネルギーデバイス用正極及びエネルギーデバイス
JP6774415B2 (ja) リチウムイオン二次電池の正極用スラリー、リチウムイオン二次電池の正極用スラリーを用いて得られるリチウムイオン二次電池用正極およびその製造方法、並びに、リチウムイオン二次電池用正極を備えたリチウムイオン二次電池およびその製造方法
JP7272272B2 (ja) 非水系電池電極用スラリーの製造方法
WO2018155713A1 (fr) Résine pour électrode de dispositif à énergie, composition de formation d'électrode de dispositif à énergie, électrode de dispositif à énergie, et dispositif à énergie
TWI785014B (zh) 能源裝置電極用複合樹脂、能源裝置電極形成用組成物、能源裝置用正極及能源裝置
WO2014098233A1 (fr) Matériau de résine de liaison destiné à des électrodes de dispositif énergétique, électrode de dispositif énergétique et dispositif énergétique
JP2015003998A (ja) アクリルポリマー粒子の製造方法及びそれにより得られるアクリルポリマー粒子
WO2015146648A1 (fr) Pâte pour une électrode positive d'une pile secondaire au lithium-ion, électrode positive obtenue au moyen de ladite pâte, procédé de fabrication de ladite électrode, pile rechargeable au lithium-ion utilisant ladite électrode positive et procédé de fabrication de ladite pile
JPWO2019117056A1 (ja) 非水電解質電池用バインダー、それを用いたバインダー水溶液およびスラリー組成物、並びに非水電解質電池用電極および非水電解質電池
JP5760966B2 (ja) エネルギーデバイス電極用バインダ樹脂材料、エネルギーデバイス電極及びエネルギーデバイス
US20230223540A1 (en) Binder for nonaqueous secondary battery electrode and slurry for nonaqueous secondary battery electrode
JP2016143635A (ja) エネルギーデバイス電極用共重合体、及びそれを用いたエネルギーデバイス
JP7311059B2 (ja) 負極バインダー組成物、負極、及び二次電池
JP6868751B1 (ja) 非水系二次電池電極、電極スラリー、及び非水系二次電池
WO2018087897A1 (fr) Résine pour électrodes de dispositif d'énergie, composition pour la formation d'une électrode de dispositif d'énergie, électrode pour dispositif d'énergie, et dispositif d'énergie
WO2021131278A1 (fr) Électrode de batterie secondaire non aqueuse, pâte d'électrode et batterie secondaire non aqueuse
WO2021246376A1 (fr) Liant pour électrode de batterie secondaire non aqueuse, et bouillie pour électrode de batterie secondaire non aqueuse

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: 13866085

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014553228

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: 13866085

Country of ref document: EP

Kind code of ref document: A1