[go: up one dir, main page]

WO2011024789A1 - Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique - Google Patents

Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique Download PDF

Info

Publication number
WO2011024789A1
WO2011024789A1 PCT/JP2010/064249 JP2010064249W WO2011024789A1 WO 2011024789 A1 WO2011024789 A1 WO 2011024789A1 JP 2010064249 W JP2010064249 W JP 2010064249W WO 2011024789 A1 WO2011024789 A1 WO 2011024789A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
monomer
polymer
salt
group
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2010/064249
Other languages
English (en)
Japanese (ja)
Inventor
達朗 本多
別所　啓一
真坂　房澄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
JSR Corp
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 JSR Corp filed Critical JSR Corp
Priority to JP2011528790A priority Critical patent/JPWO2011024789A1/ja
Publication of WO2011024789A1 publication Critical patent/WO2011024789A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode forming composition for forming electrodes of capacitors such as electric double layer capacitors and lithium ion capacitors, secondary batteries such as lithium ion secondary batteries and nickel metal hydride secondary batteries, and other electrochemical devices.
  • the present invention relates to an electrode, a slurry for electrode formation and an electrode formed therefrom, and an electrochemical device.
  • activated carbon Since activated carbon has a large surface area, it is suitably used as an electrode active material for electrochemical devices such as lithium ion capacitors using an electric double layer formed at the interface between the electrode and the electrolyte. Therefore, in order to adhere the activated carbon to the current collector, a large amount of binder (binder) must be used. As a result, the resulting electrode has a high internal resistance. In order to solve this problem, a binder having a strong binding force is required.
  • the binder resin used as a binder for the electrode is exposed to an oxidizing atmosphere when the electrode is used as a positive electrode, and exposed to a reducing atmosphere for a long time when used as a negative electrode. It is necessary to have From this point of view, generally, as a binder used for manufacturing the electrode, an electrochemically stable fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride is used.
  • the electrodes produced using these fluororesins have a problem that the electrode active material falls off from the current collector constituting the electrodes because the binding characteristics of the fluororesins are not sufficient. .
  • a binder resin containing 10 to 55% by mass of a component derived from a conjugated diene compound and a component derived from a monofunctional aromatic vinyl compound may be used. It has been proposed (see Patent Document 1).
  • Patent Document 1 has a problem that it does not have sufficient electrochemical stability.
  • increasing the capacity of a capacitor is very important and is being studied. It is known that increasing the thickness of the electrode layer is effective as a means for increasing the capacity of the capacitor. However, when the increase in the thickness of the electrode layer is achieved, the electrode forming slurry is good. It is necessary to have coatability and leveling properties. However, when the slurry is applied as a water-based one, the surface energy of water is high, so that sufficient leveling properties cannot be obtained, and in some cases, repelling occurs, making uniform coating difficult. In order to deal with such problems, usually, a method is adopted in which the slurry has an appropriate viscosity using carboxymethylcellulose (CMC) or the like, thereby obtaining high leveling properties.
  • CMC carboxymethylcellulose
  • the conventional electrode-forming composition has a problem that the adhesiveness to the current collector constituting the electrode is low and a slurry capable of obtaining high leveling properties cannot be obtained.
  • the present invention has been made in consideration of the above-described circumstances, and the object thereof is to obtain an excellent electrode layer with excellent leveling properties and excellent adhesion to a current collector. It is providing the composition for electrode formation.
  • Another object of the present invention is to provide an electrode-forming slurry, an electrode and an electrochemical device using the above composition.
  • a slurry containing a modifying polymer made of a polymer having a sulfonic acid (salt) group is contained together with a binder resin.
  • the present invention has been completed by finding that an electrode layer having improved coating properties and leveling properties and excellent adhesion to a current collector can be formed.
  • the electrode-forming composition of the present invention is characterized by comprising (A) a modifying polymer having a sulfonic acid (salt) group and (B) a binder resin.
  • the amount of the (A) modifying polymer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the (B) binder resin.
  • the polymer which forms the (A) modifying polymer is a copolymer having a block structure.
  • the polymer forming the (A) modifying polymer is preferably obtained by polymerizing a monomer having a sulfonic acid (salt) group. And the polymer which forms the polymer for modification (A), (A) a monomer having a sulfonic acid (salt) group, and (B) by at least one monomer selected from the group consisting of a monomer having a carboxylic acid (salt) group, a monomer having a hydroxyl group, and a monomer having a skeleton derived from ethylene oxide or propylene oxide A copolymer is preferred.
  • the (A) modifying polymer contains a component of a monomer having a carboxylic acid (salt) group, and the content thereof is less than 20 mol%.
  • the monomer (a) having a sulfonic acid (salt) group is preferably isoprenesulfonic acid (salt) or (meth) acrylamido-2-methylpropanesulfonic acid (salt). Further, the monomer having a carboxylic acid (salt) group is preferably itaconic acid (salt).
  • the slurry for electrode formation of this invention is characterized by including said electrode formation composition, (C) dispersion medium, and (D) electrode active material.
  • the electrode of the present invention is characterized in that it has an electrode layer formed on at least one surface of the current collector by the electrode forming slurry.
  • the electrochemical device of the present invention comprises the above electrode.
  • composition for forming an electrode of the present invention a good coating property and excellent leveling property can be obtained in a slurry of the composition, and an electrode layer having excellent adhesion to a current collector can be formed. .
  • Electrode-forming composition The electrode-forming composition of the present invention (hereinafter, also simply referred to as “electrode-forming composition”) is a modifying polymer comprising (A) a polymer having a sulfonic acid (salt) group. (Hereinafter also referred to as “component (A)”) and (B) a binder resin (hereinafter also referred to as “component (B)”), and usually in (C) the dispersion medium.
  • component (A) a polymer having a sulfonic acid (salt) group.
  • component (B) a binder resin
  • C the dispersion medium
  • the modification polymer is a polymer having a sulfonic acid (salt) group.
  • Production method 1 of component (A) The modifying polymer that is a component of the electrode-forming composition of the present invention is a polymer having a sulfonic acid (salt) group, and the sulfonic acid (salt) group-containing polymer is, for example, a diene structure or an aromatic. A method in which a part or all of the aromatic ring or residual double bond of the precursor is sulfonated or a part or all of the diene structure is hydrogenated after the base polymer containing the group structure is used as a precursor. It can be obtained by a method.
  • a known hydrogenation catalyst can be used.
  • a hydrogenation catalyst or a hydrogenation method described in JP-A-5-222115 can be used.
  • the base polymer may be a random type or a block type copolymer such as AB type or ABA type without particular limitation.
  • a block copolymer is used as the base polymer, a copolymer having a sulfonic acid (salt) group having a block structure is obtained.
  • the isoprene unit can be preferentially sulfonated by using a sulfuric anhydride / electron donating compound described later, and the styrene-isoprene block copolymer After hydrogenation of the combined isoprene unit, the aromatic ring of styrene is preferentially sulfonated with sulfuric anhydride to obtain a copolymer having a sulfonic acid (salt) group block and a hydrophobic block.
  • Preferred base polymers include, for example, polystyrene, isoprene homopolymer, butadiene homopolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene ternary block copolymer, butadiene-styrene. Random copolymers, butadiene-styrene block copolymers, styrene-butadiene-styrene block copolymers, hydrogenated products of these polymers, ethylene-propylene-diene terpolymers, and the like are more preferable.
  • polystyrene styrene-isoprene random copolymers
  • styrene-isoprene block copolymers styrene-isoprene block copolymers and their water. It is an additive.
  • the double bond portion in the polymer is sulfonated by a sulfonating agent.
  • a sulfonating agent By this sulfonation, the double bond is opened to become a single bond, or a hydrogen atom is replaced with a sulfonic acid group while the double bond remains.
  • sulfuric acid anhydride a complex of sulfuric acid anhydride and an electron donating compound
  • sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, hydrogen sulfite (Na salt, K salt, Li salt, etc.) are preferably used.
  • Examples of the electron donating compound include ethers such as N, N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, and diethyl ether; amines such as pyridine, piperazine, trimethylamine, triethylamine, and tributylamine; dimethyl sulfide, diethyl sulfide And nitrile compounds such as acetonitrile, ethyl nitrile, and propyl nitrile.
  • N, N-dimethylformamide and dioxane are preferable.
  • the amount of the sulfonating agent used is usually 0.2 to 2.0 mol, preferably 0.3 to 1.2 mol in terms of sulfuric anhydride, based on 1 mol of the diene unit in the base polymer. If the amount is less than 2 mol, it is difficult to obtain the desired sulfonic acid polymer. On the other hand, if the amount exceeds 2.0 mol, the amount of residual sulfonating agent such as unreacted sulfuric anhydride increases, and the sulfuric acid after neutralization with alkali This is not preferable because a large amount of salt is produced and the purity of the product is lowered.
  • a solvent inert to a sulfonating agent such as sulfuric anhydride can be used.
  • the solvent include halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, and dichloromethane; nitromethane, Nitro compounds such as nitrobenzene; aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane. These solvents can be used as a mixture of two or more.
  • the reaction temperature of this sulfonation is usually ⁇ 70 to + 200 ° C., preferably ⁇ 30 to + 50 ° C. If the temperature is lower than ⁇ 70 ° C., the sulfonation reaction becomes slow and is not economical. Since reaction may occur and the product may be blackened or insolubilized, it is not preferable. In this way, an intermediate in which a sulfonating agent such as sulfuric anhydride is bonded to the base polymer (a sulfonate of the base polymer, hereinafter referred to as “intermediate”) is formed.
  • a sulfonating agent such as sulfuric anhydride
  • a double bond is opened by allowing water or a basic substance to act on this intermediate, so that the sulfonic acid group is formed. It becomes a bonded single bond or is obtained by replacing a hydrogen atom with a sulfonic acid group while leaving a double bond.
  • Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium-t-butoxide, potassium-t-butoxide, etc.
  • Alkali metal alkoxides carbonates such as sodium carbonate, potassium carbonate, lithium carbonate; methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium bromide, propyl magnesium
  • Organometallic compounds such as iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum; ammonia water, trimethylamine, triethylamine Include sodium, lithium, potassium, calcium, metals such as zinc; tripropylamine, tributylamine, pyridine, aniline, amines such as piperazine.
  • These basic substances can be used alone or in combination of two or more. Among these basic substances, alkali metal hydroxides and ammonia water are preferable, and sodium hydroxide and lithium hydroxide are particularly preferable.
  • the amount of the basic substance used is 2 mol or less, preferably 1.3 mol or less with respect to 1 mol of the sulfonating agent used. When the amount exceeds 2 mol, the amount of unreacted basic material increases, and the product This is not preferable because the purity of the resin decreases.
  • the basic substance can be used in the form of an aqueous solution, or can be used after being dissolved in an organic solvent inert to the basic substance.
  • organic solvent examples include the above-mentioned various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol. These solvents can be used as a mixture of two or more.
  • the concentration of the basic substance is usually 1 to 70% by mass, preferably about 10 to 50% by mass.
  • the reaction with the basic substance is usually carried out at a temperature of ⁇ 30 to + 150 ° C., preferably 0 to + 120 ° C., more preferably +50 to + 100 ° C., and can be performed under normal pressure, reduced pressure or increased pressure. Can be implemented. Further, this reaction time is usually 0.1 to 24 hours, preferably 0.5 to 5 hours.
  • the polymer having a sulfonic acid (salt) group forming the modifying polymer of the present invention may be a monomer having a sulfonic acid (salt) group (hereinafter referred to as “specific monomer”) in addition to the above-described method. And, if necessary, can be obtained by polymerizing a monomer component composed of a specific monomer and another monomer.
  • Specific monomers include, for example, isoprene sulfonic acid, (meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, allyl Sulfonic acid, isoamylene sulfonic acid, unsaturated (meth) allyl ether monomer represented by the following general formula (1) [for example, 3-allyloxy-2-hydroxypropanesulfonic acid, 3-metaallyloxy-2- Hydroxypropane sulfonic acid
  • the 2 H 4 ) unit and the (OC 3 H 6 ) unit are bonded in any order, Y and Z are sulfonic acid groups or hydroxyl groups, and at least one of Y and Z is a sulfonic acid group.
  • R 2 to R 7 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO 3 X (where X is a hydrogen atom, a metal atom, an ammonium group) Or at least one of R 2 to R 7 is —SO 3 X),
  • These sulfonic acid (salt) group-containing monomers can be used singly or in combination of two or more.
  • the ratio of the monomer component having a sulfonic acid (salt) group in the modifying polymer of the present invention is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, particularly preferably 50 to 100 mol%. It is.
  • a polymer having a sulfonic acid (salt) group that forms the modifying polymer of the present invention includes a carboxylic acid (salt) together with the specific monomer.
  • the monomer having a carboxylic acid (salt) group is not particularly limited as long as it is a monomer having a polymerizable double bond containing a carboxylic acid group.
  • These salts include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and octyl (meth) acrylate, preferably itaconic acid, itaconic anhydride, Acrylic acid, methacrylic acid or salts thereof.
  • Examples of the monomer having a hydroxyl group include unsaturated alcohols such as vinyl alcohol, allyl alcohol, methyl vinyl alcohol, ethyl vinyl alcohol, vinyl glycolic acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polytetramethylene glycol Di (meth) acrylate, butanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, pentaerythritol (Meth) acrylate, hydroxyl group-containing such as hydroxypropyl phenoxyethyl (meth) acrylate (me
  • Examples of the monomer having a skeleton derived from ethylene oxide or propylene oxide include polyoxyethylene monomethacrylate (1 to 10 mol adduct of alkylene oxide) and a compound having a structure represented by the following general formula (3)
  • R 8 is a hydrogen atom or a methyl group
  • R 9 is an aliphatic group or an aromatic group having 1 to 18 carbon atoms
  • A is a methylene group, a propylene group, or a tetramethylene group.
  • preferred is polyoxyethylene monomethacrylate (ethylene oxide 5 mol adduct). 1 type (s) or 2 or more types can be used for said monomer.
  • the polymer having a sulfonic acid (salt) group that forms the modifying polymer of the present invention can be obtained by copolymerizing other monomers that can be copolymerized in addition to the above monomer components.
  • Other monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, p-methylstyrene, butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3.
  • -Aliphatic conjugated dienes such as butadiene and vinyl cyanide compounds such as (meth) acrylonitrile.
  • These monomers can use 1 type (s) or 2 or more types. When these other monomers are copolymerized, it is preferably 30 mol% or less based on the total monomers.
  • the polymer for modifying the component (A) is preferably a homopolymer of a specific monomer or a copolymer of the specific monomer and a monomer having a carboxylic acid (salt) group. And a copolymer of a specific monomer, a monomer having a carboxylic acid (salt) group, and a monomer having a hydroxyl group.
  • the content ratio of the component by the monomer having a carboxylic acid (salt) group is preferably less than 90 mol%, More preferably, it is 85 to 5 mol%, particularly preferably 80 to 10 mol%.
  • a specific monomer (sulfonic acid (sulfonic acid) group is, for example, as follows. That is, the composition of the monomer component is subjected to a normal reaction temperature of 20 to 200 ° C., preferably 40 to 150 ° C. in the presence of a known polymerization initiator such as hydrogen peroxide, sodium persulfate, or potassium persulfate.
  • the desired polymer can be produced by carrying out the polymerization reaction for a reaction time of 0.1 to 20 hours, preferably 1 to 15 hours.
  • the polymerization can be carried out by sequentially adding monomer components used for the polymerization.
  • the “sequential polymerization” is a polymerization method in which the monomer component is charged into the polymerization system within a predetermined time by a constant amount per unit time or by changing the addition amount.
  • a polymerization solvent can be used in order to carry out the reaction smoothly.
  • the polymerization solvent water or a mixture of water and an organic solvent that can be mixed with water can be used.
  • Specific examples of the organic solvent are not particularly limited as long as they can be mixed with water, and examples thereof include tetrahydrofuran, 1,4-dioxane, alcohols, and the like.
  • the polymer having a sulfonic acid (salt) group forming the modifying polymer of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 3 3,000 to 300,000, more preferably 5,000 to 300,000.
  • a polymer having a weight average molecular weight exceeding 500,000 is usually difficult to handle because it is gelled.
  • the modifying polymer of the component (A) of the present invention may be a polymer having a counter ion of a cationic species other than hydrogen.
  • the cationic species is not particularly limited, but alkali metals, alkaline earth metals, ammonium, amines and the like are preferable.
  • alkali metal include sodium and potassium
  • examples of the alkaline earth metal include calcium and magnesium
  • examples of the amine include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, and tributylamine.
  • Examples thereof include polyamines such as alkylamine, ethylenediamine, diethylenetriamine and triethylenetetramine, morpholine, piperidine and the like. Preferred are potassium, ammonium and alkylamine.
  • a monomer having a preferred cationic species may be polymerized, or after copolymerization of an acid type monomer, with a corresponding alkali medium. May be summed up. It is also possible to exchange the polymer (salt) with other kinds of cationic species by various ion exchange techniques. These cationic species can be used alone or in combination of two or more.
  • the modifying polymer for the component (A) is usually 1 with respect to 100 parts by mass of the binder resin (B) described later. It is used in an amount of ⁇ 50 parts by mass, preferably 2 to 50 parts by mass, particularly preferably 3 to 40 parts by mass.
  • the content of the modifying polymer is within the above range, it is possible to provide a slurry that is excellent in adhesion to the current collector constituting the electrode and has excellent film thickness uniformity due to good leveling properties.
  • An electrode forming composition can be provided.
  • the slurry has poor leveling properties, and the adhesion of the resulting electrode layer tends to deteriorate.
  • the content of the component (A) is excessive, even if the leveling property is good, the relative ratio of the binder resin is lowered, so that sufficient adhesion tends not to be obtained.
  • the component (B) is a binder resin and is a component that functions as a binder.
  • this (B) component what is used for a general battery electrode binder, a capacitor electrode binder, etc. is employable.
  • Preferable examples of the component (B) include styrene butadiene polymers, (meth) acrylic polymers, fluorine polymers, and composites of fluorine polymers and (meth) acrylic polymers.
  • these binder resin can be used individually by 1 type or in combination of 2 or more types.
  • the styrene butadiene polymer is a polymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound as essential structural units.
  • the (meth) acrylic polymer is a polymer having at least one of a structural unit derived from an acrylate ester and a structural unit derived from a methacrylic acid ester as an essential structural unit.
  • the fluorine-based polymer is a polymer having a structural unit derived from a polymerizable compound (fluorine-based monomer) containing a fluorine atom as an essential structural unit.
  • (meth) acrylic acid means both “acrylic acid” and “methacrylic acid”.
  • ⁇ (meth) acrylate means both “ ⁇ acrylate” and “ ⁇ methacrylate”.
  • the component (B) is a polymer having a structural unit derived from a polymerizable monomer such as a conjugated diene compound, an aromatic vinyl compound, a (meth) acrylate compound, an ethylenically unsaturated compound, and a fluorine-based monomer. Is preferred. In addition, these polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.
  • a polymerizable monomer such as a conjugated diene compound, an aromatic vinyl compound, a (meth) acrylate compound, an ethylenically unsaturated compound, and a fluorine-based monomer. Is preferred.
  • these polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.
  • conjugated diene compound examples include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene and the like. Of these, 1,3-butadiene is preferred. These conjugated diene compounds can be used singly or in combination of two or more.
  • Aromatic vinyl compound Specific examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like. Of these, styrene is preferred. These aromatic vinyl compounds can be used singly or in combination of two or more.
  • (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n -Butyl (meth) acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-hexyl (meth) acrylate, octyl (meth) acrylate I-nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, and the like.
  • methyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is more preferable.
  • These (meth) acrylate compounds can be used alone or in combination of two or more.
  • Ethylenically unsaturated carboxylic acid Specific examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid and itaconic acid.
  • Fluorine monomer Specific examples of the fluorine monomer include vinylidene fluoride, hexafluoropropylene, vinyl fluoride, tetrafluoroethylene, perfluoroalkyl vinyl ether, fluoroalkyl (meth) acrylate, and the like. Can be mentioned. Of these, vinylidene fluoride, propylene hexafluoride, tetrafluoroethylene, and fluoroalkyl (meth) acrylate are preferable. These fluorine-type monomers can be used individually by 1 type or in combination of 2 or more types.
  • the electrode is required to have oxidation resistance, and in order to meet this requirement, it is effective to use a polymer in which a structural unit derived from a fluorinated monomer is introduced as a binder resin.
  • a polymer in which a structural unit derived from a fluorinated monomer is introduced as a binder resin.
  • the monomer composition as a raw material for producing the component (B) includes monomers other than the polymerizable monomers described above, Those copolymerizable with the monomer (hereinafter also referred to as “copolymerizable compound”) may be included.
  • copolymerizable compounds include: alkyl amides of ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylol acrylamide; vinyl carboxylic acid esters such as vinyl acetate and vinyl propionate; ethylenically unsaturated dicarboxylic acids Acid anhydrides, monoalkyl esters or monoamides; aminoalkyl amides of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide; (meth) acrylonitrile, ⁇ -chloroacrylonitrile, etc. And vinyl cyanide compounds. These copolymerizable compounds can be used singly or in combination of two or more.
  • the ratio of the conjugated diene compound contained in the monomer composition is 20 to 58% by mass. Preferably, it is 30 to 55% by mass.
  • the content ratio of the conjugated diene compound is less than 20% by mass, the resulting copolymer has a high glass transition temperature, and the flexibility of the formed electrode layer and the adhesion of the electrode layer to the current collector are reduced. Tend to.
  • the content ratio of the conjugated diene compound exceeds 58% by mass, the surface of the electrode layer to be formed tends to be gradually sticky, so that the electrode layer sticks to the roll during press working. Tend to decrease.
  • the proportion of the aromatic vinyl compound contained in the monomer composition is preferably 10 to 55% by mass, and more preferably 20 to 50% by mass.
  • the content ratio of the aromatic vinyl compound is less than 20% by mass, for example, the interaction with graphite used as an electrode active material is lowered, and the graphite tends to easily fall off from the formed electrode layer. .
  • the content of the aromatic vinyl compound exceeds 55% by mass, the resulting polymer tends to be hard and brittle, and the flexibility of the formed electrode layer and the adhesion of the electrode layer to the current collector are reduced. Tend to.
  • the polymer used as the binder resin may contain components other than the conjugated diene compound and the aromatic vinyl compound.
  • examples of such monomers include (meth) acrylate compounds and ethylenically unsaturated carboxylic acids.
  • the proportion of the (meth) acrylate compound contained in the monomer composition is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass.
  • the content ratio of the (meth) acrylate compound is less than 5% by mass, the affinity of the resulting polymer with the electrolytic solution is lowered, and the binder tends to be an electrical resistance component, and the internal resistance of the battery tends to increase. .
  • the ratio of the ethylenically unsaturated carboxylic acid contained in the monomer composition for obtaining the binder resin is preferably 0.5 to 6% by mass, and more preferably 1 to 5% by mass. .
  • the content of the ethylenically unsaturated carboxylic acid is less than 0.5% by mass, the dispersion stability of the polymer particles (polymer particles) is insufficient when preparing the electrode-forming composition, and the aggregates It tends to occur. For this reason, there exists a tendency for the problem of the adhesiveness of the electrode layer with respect to a collector to fall easily to arise.
  • the (meth) acrylic polymer may contain a component by a monomer other than the above (meth) acrylate compound.
  • monomers include aromatic vinyl compounds and vinyl cyanide compounds.
  • the ratio of the aromatic vinyl compound contained in the monomer composition is preferably 0 to 20% by mass, and more preferably 0 to 10% by mass. If the content of the aromatic vinyl compound exceeds 20% by mass, the resulting electrode (electrode plate) is likely to be insufficient in flexibility and may crack.
  • the proportion of vinyl cyanide contained in the monomer composition for obtaining the binder resin is preferably 0 to 30% by mass, and more preferably 0 to 20% by mass. If the vinyl cyanide content exceeds 30% by mass, the flexibility of the electrode (electrode plate) tends to be insufficient, and cracks may occur. Further, the ratio of the ethylenically unsaturated carboxylic acid contained in the monomer composition is preferably 0.5 to 6% by mass, and more preferably 1 to 5% by mass.
  • the content of the ethylenically unsaturated carboxylic acid is less than 0.5% by mass, the dispersion stability of the polymer particles (polymer particles) is insufficient when preparing the electrode-forming composition, and the aggregates It tends to occur easily.
  • the content ratio of the ethylenically unsaturated carboxylic acid exceeds 6% by mass, the viscosity of the prepared electrode-forming composition may increase with time during the storage process, and the coating property tends to decrease. .
  • the proportion of vinylidene fluoride contained in the monomer composition is preferably 85 to 100% by mass.
  • the content ratio of vinylidene fluoride is less than 85% by mass, the adhesion of the electrode layer to the current collector may be lowered, and the electrode layer tends to be easily peeled off.
  • the fluoropolymer may contain tetrafluoroethylene in the monomer composition.
  • the proportion of tetrafluoroethylene contained in the monomer composition is preferably 0 to 5% by mass. If the content ratio of tetrafluoroethylene exceeds 5% by mass, the flexibility of the electrode (electrode plate) tends to be insufficient, and cracks may occur.
  • the proportion of propylene hexafluoride contained in the monomer composition is preferably 0 to 10% by mass. When the content ratio of hexafluoropropylene exceeds 10% by mass, the adhesion of the electrode layer to the current collector may be lowered, and the electrode layer tends to be easily peeled off.
  • this fluorine-based polymer may contain a component due to a monomer other than the above-mentioned fluorine-based monomer in the monomer composition.
  • a fluoropolymer and a (meth) acrylic polymer obtained by polymerizing the above (meth) acrylate compound using a fluoropolymer as a seed. It is preferable to use the composite as the component (B).
  • the binder resin of component (B) preferably forms polymer particles and is contained in the electrode forming composition in a latex state.
  • the number average particle diameter of the polymer particles contained in the latex is preferably 70 to 350 nm, and more preferably 80 to 300 nm.
  • the polymer particles move to the surface of the coating layer when the coating layer made of the electrode forming composition applied on the surface of the current collector is dried.
  • the surface of the electrode layer to be formed is preferable because it does not easily become sticky. For this reason, an electrode layer becomes difficult to peel at the time of press work.
  • the glass transition temperature (Tg) of the binder resin constituting the component (B) is preferably ⁇ 40 to 50 ° C., more preferably ⁇ 35 to 30 ° C.
  • the glass transition temperature of the binder resin is within the above range, an excessive increase in the adhesiveness of the electrode plate surface is suppressed. For this reason, sticking to a roll is difficult to occur during press working, and as a result, peeling of the electrode layer can be suppressed.
  • it is preferable in that the flexibility of the electrode layer to be formed is ensured and cracks are hardly generated in the electrode layer.
  • (C) Dispersion medium In the electrode-forming composition of the present invention, the (A) component, the (B) component, and “other components” blended as necessary are the (C) component. Dispersed in a dispersion medium. Water can be used as the dispersion medium. As described above, when the component (B) forms polymer particles and is contained in the electrode-forming composition in a latex state, this latex can be prepared by emulsion polymerization. For this reason, the water used at the time of emulsion polymerization can be used as the dispersion medium of the component (C) as it is, or the water used at the time of emulsion polymerization can be used as it is as the dispersion medium.
  • water as a dispersion medium may be replaced with an organic dispersion medium suitable for the electrode active material, if necessary.
  • an organic dispersion medium for example, aromatic hydrocarbon compounds, non-aromatic hydrocarbon compounds, chlorine-containing hydrocarbon compounds, nitrogen-containing hydrocarbon compounds, sulfur-containing hydrocarbon compounds and the like can be used.
  • Specific examples of the organic dispersion medium include toluene, N-methylpyrrolidone (NMP), methyl isobutyl ketone (MIBK), cyclohexanone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and the like.
  • a method for replacing water with an organic dispersion medium is not particularly limited. (1) A method of adding an organic dispersion medium to latex prepared by emulsion polymerization and volatilizing water by vacuum distillation, (2) A method of volatilizing water from latex and redispersing the obtained solid in an organic dispersion medium is preferred.
  • the component (D) is an electrode active material.
  • the electrode active material include activated carbon, activated carbon fiber, silica, alumina and the like.
  • carbon materials such as graphite, non-graphitizable carbon, hard carbon, coke, etc .; polyacene organic semiconductor (PAS) And the like.
  • the total amount of the component (A) and the component (B) contained in the electrode forming composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (D).
  • the amount is preferably 0.3 to 4 parts by mass.
  • the method for preparing the electrode forming composition is not particularly limited. For example, it can be prepared by mixing the components (A) to (D) with additives (other components) blended as necessary. Specifically, for example, a mixture is prepared by adding the component (D) to the component (B) in advance, and this mixture is mixed with the component (A), or the component (D) (A).
  • the composition for electrode formation can be prepared by adding the component (B) and the component (B).
  • a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used. This mixing is preferably performed under reduced pressure. By mixing each component under reduced pressure, it is possible to prevent bubbles from being generated in the electrode layer formed using the obtained electrode forming composition.
  • the solid content concentration of the mixture is preferably 20 to 53% by mass, and preferably 25 to 50% by mass. Further preferred. When the solid content concentration exceeds 53% by mass, the viscosity of the mixture becomes high, and handling in a blending process such as metering may be difficult. On the other hand, when the solid content concentration is less than 20% by mass, the content ratio of the solid content of the obtained electrode-forming composition is lowered, and it may be difficult to form an electrode layer having a desired thickness. .
  • the suitable solid content concentration of the electrode forming composition generally varies depending on the type of electrode to be produced.
  • the solid content concentration in the electrode forming composition is preferably 30 to 60% by mass.
  • the solid content concentration of the capacitor electrode composition is preferably 20 to 40% by mass.
  • the “solid content” refers to a component obtained by removing the dispersion medium from all the components contained in the electrode forming composition.
  • Electrode The electrode of the present invention comprises a current collector and an electrode layer formed by applying the above-mentioned electrode forming composition onto the surface of the current collector and drying it.
  • the electrode layer of the electrode of the present invention is formed using the above electrode forming composition. Therefore, the electrode of the present invention has the characteristics that the adhesion strength between the current collector and the electrode layer is high and the film thickness is excellent.
  • the current collector metal foil, etching metal foil, expanded metal, or the like can be used.
  • the material constituting the current collector include metal materials such as aluminum, copper, nickel, tantalum, stainless steel, and titanium. An appropriate material may be selected from these metal materials according to the type of electrochemical device to be manufactured.
  • the thickness of the current collector may be set as appropriate according to the type of electrochemical device to be manufactured. For example, when producing an electrode for an electric double layer capacitor, the thickness of the electrode layer is preferably 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • Electrode layer The electrode layer can be formed by applying the above-mentioned electrode forming composition onto the surface of the current collector to form a coating layer (coating layer) and then drying. You may press-process as needed, after drying a coating layer.
  • the method for applying the electrode forming composition on the surface of the current collector include a doctor blade method, a reverse roll method, a comma bar method, a gravure method, and an air knife method.
  • the temperature for drying the coated film is preferably 20 to 250 ° C., more preferably 50 to 150 ° C.
  • the drying time of the coating layer is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.
  • a processing machine such as a high pressure super press, a soft calender, or a one-ton press can be used for the pressing.
  • the conditions for press working are appropriately set according to the processing machine to be used.
  • the thickness of the electrode layer thus formed is usually 40 to 100 ⁇ m.
  • the density of the electrode layer is usually 1.3 to 2.0 g / cm 2 .
  • Electrochemical device The electrochemical device of the present invention comprises the above-described electrode. That is, the electrochemical device of the present invention has high product reliability because it has an electrode with high adhesion strength between the current collector and the electrode layer and high leveling of the electrode layer.
  • electrochemical devices include electric double layer capacitors, capacitors such as lithium ion capacitors, secondary batteries such as lithium ion secondary batteries and nickel metal hydride secondary batteries, and others.
  • the electrochemical device is a lithium ion capacitor
  • an electrolytic solution in which a lithium compound as an electrolyte is dissolved in a solvent is used as the electrolytic solution.
  • the electrolyte LiClO 4, LiBF 4, LiI , LiPF 6, LiCF 3 SO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3
  • Examples include LiC 4 F 9 SO 3 , Li (C 4 F 3 SO 2 ) 2 N, Li [CO 2 ) 2 ] 2 B, and the like.
  • the solvent for the electrolyte include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as ⁇ -butyrolactone; trimethoxysilane, 1,2-dimethoxy Ethers such as ethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; acetonitrile, Nitrogen-containing compounds such as nitromethane; esters such as methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triester; diglyme, triglyme, Glymes such as trag
  • the capacitor is an electric double layer capacitor
  • an electrolytic solution in which an electrolyte for the electric double layer capacitor is dissolved in the above solvent is used.
  • the electrolyte for the electric double layer capacitor include tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate, and the like.
  • the weight average molecular weight (Mw) is obtained by converting the result determined by gel permeation chromatography (GPC) using a calibration curve prepared using sodium polystyrene sulfonate as a standard sample.
  • the measurement conditions of GPC are as follows. Column (1): G3000PWXL [manufactured by Tosoh Corporation] Column (2): GMPWXL [manufactured by Tosoh Corporation] Column (3): GMPWXL [manufactured by Tosoh Corporation] Columns (1) to (3) are connected in series in this order, and a sample is introduced from the column (1) side.
  • Example 7 In Example 4 above, in place of 500 g of 20% aqueous sodium styrenesulfonate solution, 305 g of 20% aqueous sodium acrylamide-2-methylpropanesulfonate and 130 g of 30% aqueous itaconic acid were used. In the same manner as in Production Example 4, a sodium acrylamido-2-methylpropanesulfonate / itaconic acid (50/50 molar ratio) copolymer (G) was obtained. The copolymer had a weight average molecular weight of 8,000.
  • Example 4 instead of 500 g of 20% aqueous sodium styrenesulfonate solution, 64 g of 20% aqueous sodium acrylamide-2-methylpropanesulfonate and 7 g of 20% aqueous acrylic acid solution were used.
  • a sodium acrylamido-2-methylpropanesulfonate / acrylic acid (85/15 molar ratio) copolymer (K) was obtained.
  • the copolymer had a weight average molecular weight of 10,000.
  • Example 15 In Example 4 above, instead of 500 g of 20% sodium styrenesulfonate aqueous solution, 373 g of 20% sodium acrylamide-2-methylpropanesulfonate aqueous solution and 127 g of 20% aqueous acrylic acid solution were used. In the same manner as in Production Example 4, a sodium acrylamide-2-methylpropanesulfonate / acrylic acid (50/50 molar ratio) copolymer (O) was obtained. The copolymer had a weight average molecular weight of 12,000.
  • the reaction liquid was cooled and the stirring was stopped, the unreacted monomer was released to stop the reaction, and a fluoropolymer latex was obtained.
  • 150 parts of the above fluoropolymer latex (in terms of solid content) and 2- (1-allyl) -4-nonylphenoxypolyethylene glycol sulfate as an emulsifier 3 parts of fetoammonium was charged and the temperature was raised to 75 ° C.
  • Electrode for evaluation (1) Electric double layer capacitor general electrode (1) Activated carbon “Kuraray Coal YP” (manufactured by Kuraray Chemical Co., Ltd.) 100 parts, conductive carbon “Denka Black” (manufactured by Denki Kagaku Kogyo Co., Ltd.), 2 parts carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.), fluoropolymer ( 4 parts of a binder resin made of a composite (1) of a (meth) acrylic polymer, and 1 part of a modifying polymer made of the copolymer (M) according to Production Example 13 above, a slurry solid content concentration of 25%.
  • Kuraray Coal YP manufactured by Kuraray Chemical Co., Ltd.
  • conductive carbon “Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • carboxymethyl cellulose manufactured by Daicel Chemical Industries, Ltd.
  • fluoropolymer 4 parts of a binder resin made of
  • This evaluation electrode forming slurry was uniformly applied on the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method. After drying for 15 minutes at a temperature of 120 ° C. using a dryer, further drying under reduced pressure at 5 mmHg and 150 ° C. for 2 hours using a vacuum dryer contains activated carbon on one side of the current collector made of aluminum foil. An electrode for evaluation (2) on which an electrode layer to be formed was formed was obtained.
  • Electrode for lithium ion capacitor positive electrode 92 parts of activated carbon “Kuraray Coal YP” (manufactured by Kuraray Chemical Co., Ltd.), 6 parts of conductive carbon “Denka Black” (manufactured by Denki Kagaku Kogyo), carboxymethylcellulose (manufactured by Daicel Chemical Industries) 4 parts, 4 parts of a binder resin made of a composite (1) of a fluoropolymer and a (meth) acrylic polymer, and 1 part of a modifying polymer made of the copolymer (M) according to Production Example 13 above
  • a uniform slurry for electrode formation for evaluation was prepared.
  • This evaluation electrode forming slurry was uniformly applied on the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method. After drying for 15 minutes at a temperature of 120 ° C. using a dryer, further drying under reduced pressure at 5 mmHg and 150 ° C. for 2 hours using a vacuum dryer contains activated carbon on one side of the current collector made of aluminum foil. An electrode for evaluation (3) on which an electrode layer to be formed was formed was obtained.
  • Electrode for evaluation (5) Electric double layer capacitor general electrode 1 Activated carbon “Kuraray Coal YP” (manufactured by Kuraray Chemical Co., Ltd.) 100 parts, conductive carbon “Denka Black” (manufactured by Denki Kagaku Kogyo Co., Ltd.), 2 parts carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.), fluoropolymer ( For forming a uniform electrode for evaluation by adding and stirring 5 parts of a binder resin made of a composite (1) of a (meth) acrylic polymer and adding ion-exchanged water so that the slurry solid content concentration becomes 25%. A slurry was prepared.
  • Kuraray Coal YP manufactured by Kuraray Chemical Co., Ltd.
  • conductive carbon “Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • carboxymethyl cellulose manufactured by Daicel Chemical Industries, Ltd.
  • fluoropolymer For forming a uniform electrode
  • This evaluation electrode forming slurry was uniformly applied on the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method. After drying for 15 minutes at a temperature of 120 ° C. using a dryer, further drying under reduced pressure at 5 mmHg and 150 ° C. for 2 hours using a vacuum dryer contains activated carbon on one side of the current collector made of aluminum foil. An electrode for evaluation (18) on which an electrode layer to be formed was formed was obtained.
  • Electric double layer capacitor general electrode 2 Activated carbon “Kuraray Coal YP” (manufactured by Kuraray Chemical Co., Ltd.) 100 parts, conductive carbon “Denka Black” (manufactured by Denki Kagaku Kogyo Co., Ltd.), 1.5 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries), fluoropolymer A uniform evaluation electrode is obtained by adding ion-exchanged water and stirring 5 parts of a binder resin composed of a composite (1) of (meth) acrylic polymer and slurry solids concentration of 25%. A forming slurry was prepared.
  • This evaluation electrode forming slurry was uniformly applied on the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method. After drying for 15 minutes at a temperature of 120 ° C. using a dryer, further drying under reduced pressure at 5 mmHg and 150 ° C. for 2 hours using a vacuum dryer contains activated carbon on one side of the current collector made of aluminum foil. An electrode for evaluation (19) on which an electrode layer to be formed was formed was obtained.
  • Electric double layer capacitor general electrode 3 92 parts of activated carbon “Kuraray Coal YP” (manufactured by Kuraray Chemical Co., Ltd.), 6 parts of conductive carbon “Denka Black” (manufactured by Denki Kagaku Kogyo Co., Ltd.), 4 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.), For forming a uniform electrode for evaluation by adding and stirring 5 parts of a binder resin made of a composite (1) of a (meth) acrylic polymer and adding ion-exchanged water so that the slurry solid content concentration becomes 25%. A slurry was prepared.
  • This evaluation electrode forming slurry was uniformly applied on the surface of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method. After drying for 15 minutes at a temperature of 120 ° C. using a dryer, further drying under reduced pressure at 5 mmHg and 150 ° C. for 2 hours using a vacuum dryer contains activated carbon on one side of the current collector made of aluminum foil. An electrode for evaluation (20) having an electrode layer formed thereon was obtained.
  • the evaluation electrodes (1) to (17) have an electrode layer formed of an electrode-forming slurry containing the modifying polymer of the present invention, and all have high leveling properties. It is clear that the adhesion strength of the electrode layer is high.
  • the electrodes for evaluation (18) to (20) have an electrode layer formed of an electrode forming slurry that does not contain a modifying polymer, and all of them have low leveling properties and It is clear that the adhesion strength of the electrode layer is small.

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)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention porte sur une composition pour former une électrode, qui permet la formation d'une couche d'électrode ayant de bonnes propriétés de nivellement et une excellente adhésion à un collecteur de courant. La composition pour former une électrode est caractérisée en ce qu'elle comprend (A) un polymère de modification ayant un groupe (sel) acide sulfonique et (B) une résine de liant. La quantité de polymère de modification (A) par rapport à 100 parties en masse de la résine de liant (B) est, de préférence, de 1 à 50 parties en masse. Le polymère de modification est, de préférence, un copolymère (a) d'un monomère ayant un groupe (sel) acide sulfonique et (b) d'un monomère choisi dans le groupe constitué par un monomère ayant un groupe (sel) acide carboxylique, un monomère ayant un groupe hydroxy et un monomère ayant un squelette issu d'un oxyde éthylène ou d'un oxyde de propylène.
PCT/JP2010/064249 2009-08-24 2010-08-24 Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique Ceased WO2011024789A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011528790A JPWO2011024789A1 (ja) 2009-08-24 2010-08-24 電極形成用組成物、電極形成用スラリー、電極および電気化学デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009192891 2009-08-24
JP2009-192891 2009-08-24

Publications (1)

Publication Number Publication Date
WO2011024789A1 true WO2011024789A1 (fr) 2011-03-03

Family

ID=43627894

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/064249 Ceased WO2011024789A1 (fr) 2009-08-24 2010-08-24 Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique

Country Status (2)

Country Link
JP (1) JPWO2011024789A1 (fr)
WO (1) WO2011024789A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128182A1 (fr) * 2011-03-18 2012-09-27 日本ゼオン株式会社 Composition barbotine pour électrode négative de pile secondaire au lithium ion, électrode négative de pile secondaire au lithium ion, et pile secondaire au lithium ion
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
WO2013018887A1 (fr) * 2011-08-03 2013-02-07 日本ゼオン株式会社 Composition adhésive conductrice pour électrode d'élément électrochimique, collecteur comportant une couche adhésive, et électrode d'élément électrochimique
JP2013041819A (ja) * 2011-07-15 2013-02-28 Nippon Zeon Co Ltd 電気化学素子負極電極用複合粒子、電気化学素子負極電極材料、及び電気化学素子負極電極
JP2013168272A (ja) * 2012-02-15 2013-08-29 Jsr Corp 電極用バインダー組成物、電極用スラリー、電極、および蓄電デバイス
JP2014026868A (ja) * 2012-07-27 2014-02-06 Denso Corp 非水電解液二次電池用正極、及び非水電解液二次電池
CN103918111A (zh) * 2011-11-07 2014-07-09 电气化学工业株式会社 电极用粘结剂组合物
WO2014118963A1 (fr) * 2013-02-01 2014-08-07 株式会社 日立製作所 Matériau d'électrode négative pour batteries secondaires au lithium-ion
JP2015022956A (ja) * 2013-07-22 2015-02-02 Jsr株式会社 蓄電デバイス用スラリー、蓄電デバイス電極、セパレーターおよび蓄電デバイス
WO2015015598A1 (fr) * 2013-07-31 2015-02-05 株式会社日立製作所 Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative
WO2015052809A1 (fr) * 2013-10-10 2015-04-16 株式会社日立製作所 Matériau d'électrode négative pour batteries secondaires au lithium-ion, électrode négative pour batteries secondaires au lithium-ion l'utilisant, batterie secondaire au lithium-ion et système de batterie
US9685658B2 (en) 2011-07-15 2017-06-20 Zeon Corporation Composite particles for electrochemical device electrode, material for electrochemical device electrode, and electrochemical device electrode
KR20180040636A (ko) 2015-09-25 2018-04-20 가부시키가이샤 스크린 홀딩스 막두께 측정 장치 및 막두께 측정 방법
WO2019039560A1 (fr) 2017-08-24 2019-02-28 日本ゼオン株式会社 Composition de liant pour batteries secondaires non aqueuses, composition de bouillie pour couches fonctionnelles de batterie secondaire non aqueuse, couche fonctionnelle pour batteries secondaires non aqueuses, élément de batterie pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
WO2019107229A1 (fr) 2017-11-30 2019-06-06 日本ゼオン株式会社 Composition de liant pour batterie secondaire non aqueuse, composition de bouillie pour couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle de batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse, et batterie secondaire non aqueuse
JP2019110002A (ja) * 2017-12-18 2019-07-04 荒川化学工業株式会社 リチウムイオン電池用バインダー水溶液、リチウムイオン電池用電極スラリー及びその製造方法、リチウムイオン電池用電極、並びにリチウムイオン電池
KR20220147584A (ko) 2020-02-26 2022-11-03 니폰 제온 가부시키가이샤 전기 화학 소자용 복합 입자, 제조 방법, 전기 화학 소자용 전극, 및 전기 화학 소자
CN115286802A (zh) * 2022-09-30 2022-11-04 宁德时代新能源科技股份有限公司 Bab型嵌段共聚物、制备方法、粘结剂、正极极片、二次电池及用电装置
KR20230113738A (ko) 2020-11-30 2023-08-01 니폰 제온 가부시키가이샤 비수계 이차 전지 전극용 바인더 조성물, 비수계 이차 전지 전극용 슬러리 조성물, 비수계 이차 전지용 전극 및 비수계 이차 전지
US11817582B2 (en) 2018-01-04 2023-11-14 Lg Chem, Ltd. Binder composition for secondary battery, and electrode slurry composition, electrode and secondary battery including same
EP4571916A4 (fr) * 2022-08-12 2026-01-07 Lg Energy Solution Ltd Composite électrolyte solide-électrode, procédé permettant de fabriquer un composite électrolyte solide-électrode, et batterie tout solide comprenant ledit composite électrolyte solide-électrode

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08203499A (ja) * 1995-01-25 1996-08-09 Namitsukusu Kk 導電性組成物およびそれを用いた電極
JPH09320604A (ja) * 1996-05-28 1997-12-12 Japan Synthetic Rubber Co Ltd ２次電池電極用導電性結着組成物とその製造方法
JP2002134171A (ja) * 2000-10-23 2002-05-10 Mitsubishi Chemicals Corp リチウム二次電池
JP2002319401A (ja) * 2001-04-19 2002-10-31 Hitachi Maxell Ltd 水素吸蔵合金電極用ぺースト、水素吸蔵合金電極および水素化物二次電池
WO2007088979A1 (fr) * 2006-02-02 2007-08-09 Jsr Corporation Composition polymere, pate destinee a etre utilisee dans une electrode d'accumulateur et electrode correspondante
JP2009059514A (ja) * 2007-08-30 2009-03-19 Sony Corp 負極および電池
JP2009123523A (ja) * 2007-11-15 2009-06-04 Jsr Corp 電池電極用バインダー組成物、その製造方法、電池電極用ペースト、電池電極、及び電池電極の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08203499A (ja) * 1995-01-25 1996-08-09 Namitsukusu Kk 導電性組成物およびそれを用いた電極
JPH09320604A (ja) * 1996-05-28 1997-12-12 Japan Synthetic Rubber Co Ltd ２次電池電極用導電性結着組成物とその製造方法
JP2002134171A (ja) * 2000-10-23 2002-05-10 Mitsubishi Chemicals Corp リチウム二次電池
JP2002319401A (ja) * 2001-04-19 2002-10-31 Hitachi Maxell Ltd 水素吸蔵合金電極用ぺースト、水素吸蔵合金電極および水素化物二次電池
WO2007088979A1 (fr) * 2006-02-02 2007-08-09 Jsr Corporation Composition polymere, pate destinee a etre utilisee dans une electrode d'accumulateur et electrode correspondante
JP2009059514A (ja) * 2007-08-30 2009-03-19 Sony Corp 負極および電池
JP2009123523A (ja) * 2007-11-15 2009-06-04 Jsr Corp 電池電極用バインダー組成物、その製造方法、電池電極用ペースト、電池電極、及び電池電極の製造方法

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128182A1 (fr) * 2011-03-18 2012-09-27 日本ゼオン株式会社 Composition barbotine pour électrode négative de pile secondaire au lithium ion, électrode négative de pile secondaire au lithium ion, et pile secondaire au lithium ion
KR20180126613A (ko) * 2011-03-18 2018-11-27 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물, 리튬 이온 이차 전지 부극, 및 리튬 이온 이차 전지
JPWO2012128182A1 (ja) * 2011-03-18 2014-07-24 日本ゼオン株式会社 リチウムイオン二次電池負極用スラリー組成物、リチウムイオン二次電池負極、及びリチウムイオン二次電池
KR101921169B1 (ko) * 2011-03-18 2018-11-22 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물, 리튬 이온 이차 전지 부극, 및 리튬 이온 이차 전지
KR101978463B1 (ko) 2011-03-18 2019-05-14 제온 코포레이션 리튬 이온 이차 전지 부극용 슬러리 조성물, 리튬 이온 이차 전지 부극, 및 리튬 이온 이차 전지
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
JP2013041819A (ja) * 2011-07-15 2013-02-28 Nippon Zeon Co Ltd 電気化学素子負極電極用複合粒子、電気化学素子負極電極材料、及び電気化学素子負極電極
US9685658B2 (en) 2011-07-15 2017-06-20 Zeon Corporation Composite particles for electrochemical device electrode, material for electrochemical device electrode, and electrochemical device electrode
WO2013018887A1 (fr) * 2011-08-03 2013-02-07 日本ゼオン株式会社 Composition adhésive conductrice pour électrode d'élément électrochimique, collecteur comportant une couche adhésive, et électrode d'élément électrochimique
US10014528B2 (en) 2011-08-03 2018-07-03 Zeon Corporation Conductive adhesive composition for electrochemical element electrode, collector with adhesive layer, and electrochemical element electrode
US9257239B2 (en) 2011-11-07 2016-02-09 Denka Company Limited Binder composition for electrode
KR20140099884A (ko) * 2011-11-07 2014-08-13 덴키 가가쿠 고교 가부시기가이샤 전극용 바인더 조성물
KR101969364B1 (ko) * 2011-11-07 2019-04-17 덴카 주식회사 전극용 바인더 조성물
EP2779286A4 (fr) * 2011-11-07 2015-08-05 Denki Kagaku Kogyo Kk Composition de liant pour électrode
CN103918111A (zh) * 2011-11-07 2014-07-09 电气化学工业株式会社 电极用粘结剂组合物
JP2013168272A (ja) * 2012-02-15 2013-08-29 Jsr Corp 電極用バインダー組成物、電極用スラリー、電極、および蓄電デバイス
JP2014026868A (ja) * 2012-07-27 2014-02-06 Denso Corp 非水電解液二次電池用正極、及び非水電解液二次電池
CN104956526A (zh) * 2013-02-01 2015-09-30 株式会社日立制作所 锂离子二次电池用负极材料
WO2014118963A1 (fr) * 2013-02-01 2014-08-07 株式会社 日立製作所 Matériau d'électrode négative pour batteries secondaires au lithium-ion
JP6023222B2 (ja) * 2013-02-01 2016-11-09 株式会社日立製作所 リチウムイオン二次電池用負極材料
CN104956526B (zh) * 2013-02-01 2017-03-08 株式会社日立制作所 锂离子二次电池用负极材料
JP2015022956A (ja) * 2013-07-22 2015-02-02 Jsr株式会社 蓄電デバイス用スラリー、蓄電デバイス電極、セパレーターおよび蓄電デバイス
WO2015015598A1 (fr) * 2013-07-31 2015-02-05 株式会社日立製作所 Matériau de revêtement de matériaux actifs d'électrode négative de batteries secondaires au lithium-ion, matériau actif d'électrode négative de batteries secondaires au lithium-ion revêtu dudit matériau de revêtement et batterie secondaire au lithium-ion utilisant ledit matériau actif d'électrode négative dans l'électrode négative
WO2015052809A1 (fr) * 2013-10-10 2015-04-16 株式会社日立製作所 Matériau d'électrode négative pour batteries secondaires au lithium-ion, électrode négative pour batteries secondaires au lithium-ion l'utilisant, batterie secondaire au lithium-ion et système de batterie
US10355279B2 (en) 2013-10-10 2019-07-16 Hitachi, Ltd. Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries using same, lithium ion secondary battery and battery system
KR20180040636A (ko) 2015-09-25 2018-04-20 가부시키가이샤 스크린 홀딩스 막두께 측정 장치 및 막두께 측정 방법
KR20200042898A (ko) 2017-08-24 2020-04-24 니폰 제온 가부시키가이샤 비수계 이차 전지용 바인더 조성물, 비수계 이차 전지 기능층용 슬러리 조성물, 비수계 이차 전지용 기능층, 비수계 이차 전지용 전지 부재, 및 비수계 이차 전지
WO2019039560A1 (fr) 2017-08-24 2019-02-28 日本ゼオン株式会社 Composition de liant pour batteries secondaires non aqueuses, composition de bouillie pour couches fonctionnelles de batterie secondaire non aqueuse, couche fonctionnelle pour batteries secondaires non aqueuses, élément de batterie pour batteries secondaires non aqueuses et batterie secondaire non aqueuse
US11374224B2 (en) 2017-08-24 2022-06-28 Zeon Corporation Binder composition for non-aqueous secondary battery, slurry composition for non-aqueous secondary battery functional layer, functional layer for non-aqueous secondary battery, battery component for non-aqueous secondary battery, and non-aqueous secondary battery
KR20200093543A (ko) 2017-11-30 2020-08-05 니폰 제온 가부시키가이샤 비수계 이차 전지용 바인더 조성물, 비수계 이차 전지 기능층용 슬러리 조성물, 비수계 이차 전지용 기능층, 비수계 이차 전지용 전지 부재 및 비수계 이차 전지
WO2019107229A1 (fr) 2017-11-30 2019-06-06 日本ゼオン株式会社 Composition de liant pour batterie secondaire non aqueuse, composition de bouillie pour couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle de batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse, et batterie secondaire non aqueuse
US11482707B2 (en) 2017-11-30 2022-10-25 Zeon Corporation Binder composition for non-aqueous secondary battery, slurry composition for non-aqueous secondary battery functional layer, functional layer for non-aqueous secondary battery, battery component for non-aqueous secondary battery, and non-aqueous secondary battery
JP2019110002A (ja) * 2017-12-18 2019-07-04 荒川化学工業株式会社 リチウムイオン電池用バインダー水溶液、リチウムイオン電池用電極スラリー及びその製造方法、リチウムイオン電池用電極、並びにリチウムイオン電池
JP7031278B2 (ja) 2017-12-18 2022-03-08 荒川化学工業株式会社 リチウムイオン電池用バインダー水溶液、リチウムイオン電池用電極スラリー及びその製造方法、リチウムイオン電池用電極、並びにリチウムイオン電池
US11817582B2 (en) 2018-01-04 2023-11-14 Lg Chem, Ltd. Binder composition for secondary battery, and electrode slurry composition, electrode and secondary battery including same
KR20220147584A (ko) 2020-02-26 2022-11-03 니폰 제온 가부시키가이샤 전기 화학 소자용 복합 입자, 제조 방법, 전기 화학 소자용 전극, 및 전기 화학 소자
KR20230113738A (ko) 2020-11-30 2023-08-01 니폰 제온 가부시키가이샤 비수계 이차 전지 전극용 바인더 조성물, 비수계 이차 전지 전극용 슬러리 조성물, 비수계 이차 전지용 전극 및 비수계 이차 전지
EP4571916A4 (fr) * 2022-08-12 2026-01-07 Lg Energy Solution Ltd Composite électrolyte solide-électrode, procédé permettant de fabriquer un composite électrolyte solide-électrode, et batterie tout solide comprenant ledit composite électrolyte solide-électrode
CN115286802A (zh) * 2022-09-30 2022-11-04 宁德时代新能源科技股份有限公司 Bab型嵌段共聚物、制备方法、粘结剂、正极极片、二次电池及用电装置
CN115286802B (zh) * 2022-09-30 2023-04-07 宁德时代新能源科技股份有限公司 Bab型嵌段共聚物、制备方法、粘结剂、正极极片、二次电池及用电装置

Also Published As

Publication number Publication date
JPWO2011024789A1 (ja) 2013-01-31

Similar Documents

Publication Publication Date Title
WO2011024789A1 (fr) Composition pour former une électrode, bouillie pour former une électrode, électrode et dispositif électrochimique
CN103140964B (zh) 非水系二次电池用正极合剂、使用其的非水系二次电池用正极及二次电池
CN103238243B (zh) 电极用粘结剂组合物、电极用浆料、电极、电化学设备以及电极用粘结剂组合物的制造方法及保管方法
TWI489685B (zh) Electrochemical devices and binder compositions
JP6145693B2 (ja) 電気化学素子の電極用バインダ、電気化学素子の電極用組成物、電気化学素子の電極及び電気化学素子
KR101299285B1 (ko) 전극용 결합제 조성물
WO2013105623A1 (fr) Composition de résine liante destinée à des électrodes de batterie rechargeable, suspension épaisse destinée à des électrodes de batterie rechargeable, électrode destinée à des batteries rechargeables et batterie rechargeable au lithium-ion
WO2012091001A1 (fr) Composition pour liant d'électrode de batterie à électrolyte non aqueux, électrode pour batterie à électrolyte non aqueux, et batterie à électrolyte non aqueux
TW201131872A (en) Binder composition for secondary battery, secondary battery electrode mix comprising same, and secondary battery
KR20180050280A (ko) 점착제용 조성물 및 점착 필름, 그리고 축전 디바이스용 조성물, 축전 디바이스 전극용 슬러리, 축전 디바이스 전극, 보호막용 슬러리 및 축전 디바이스
JP5365835B2 (ja) 電気化学デバイス電極用バインダー、電気化学デバイス電極用スラリーおよび電気化学デバイス電極
JPWO2019155980A1 (ja) 非水系電池電極用スラリー、並びに非水系電池電極及び非水系電池の製造方法
WO2015099021A1 (fr) Composition de liant pour électrode de cellule secondaire au lithium-ion, électrode de cellule secondaire au lithium-ion et cellule secondaire au lithium-ion
JP6266396B2 (ja) リチウムイオン二次電池負極用バインダー
JP2011040309A (ja) 電気化学デバイス電極バインダー用組成物、電気化学デバイス電極用組成物、電気化学デバイス電極、及び電気化学デバイス
JP2016213027A (ja) 非水電解液系エネルギーデバイス電極用バインダ樹脂組成物、これを用いた非水電解液系エネルギーデバイス電極及び非水電解液系エネルギーデバイス
KR102566074B1 (ko) 리튬 이차 전지 전극용 조성물
JP5359306B2 (ja) 電気化学デバイス電極バインダー用組成物、電気化学デバイス電極用組成物、電気化学デバイス電極および電気化学デバイス
TW201138195A (en) Composition for electrode binder, composition for electrode, electrode and electrochemical device
JP5057125B2 (ja) 電極用バインダー組成物、電極用スラリー、電極、及び電気化学デバイス
JP2011009116A (ja) 電気化学デバイス電極用バインダー組成物、電気化学デバイス電極用スラリー、及び電気化学デバイス電極
JP6066142B2 (ja) 電極用スラリー、電極、および電気化学デバイス

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: 10811839

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011528790

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10811839

Country of ref document: EP

Kind code of ref document: A1