WO2011024789A1 - Composition for forming electrode, slurry for forming electrode, electrode, and electrochemical device - Google Patents

Composition for forming electrode, slurry for forming electrode, electrode, and electrochemical device Download PDF

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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
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electrode
monomer
polymer
salt
acid
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PCT/JP2010/064249
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French (fr)
Japanese (ja)
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達朗 本多
別所 啓一
真坂 房澄
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Jsr株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/058Electrodes or formation of dielectric layers thereon specially adapted for double-layer capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/38Carbon pastes or blends; Binders or additives therein
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

Disclosed is a composition for forming an electrode, which enables the formation of an electrode layer having good leveling properties and excellent adhesion to a current collector. The composition for forming an electrode is characterized by comprising (A) a modification polymer having a sulfonic acid (salt) group and (B) a binder resin. The amount of the modification polymer (A) relative to 100 parts by mass of the binder resin (B) is preferably 1 to 50 parts by mass. The modification polymer is preferably a copolymer of (a) a monomer having a sulfonic acid (salt) group and (b) a monomer selected from the group consisting of a monomer having a carboxylic acid (salt) group, a monomer having a hydroxy group and a monomer having a skeleton derived from ethylene oxide or propylene oxide.

Description

Electrode-forming composition, the electrode forming slurry, electrodes and electrochemical devices

The present invention is an electric double layer capacitor, a capacitor such as a lithium ion capacitor, and a lithium ion secondary battery, a secondary battery such as nickel-hydrogen secondary battery, a composition for electrode formation for forming the electrodes of the other electrochemical devices things, an electrode slurry for forming an electrode and is formed from this, as well as an electrochemical device.

Recently, smaller and lighter electronic devices has been remarkable, with it, the demand for smaller and lighter is very strong against the battery as a power source. Various secondary battery in order to satisfy such requirements have been developed, such as nickel-hydrogen secondary battery, lithium ion secondary batteries have been put to practical use.
On the other hand, automotive, as an electric storage device that high output characteristics, such as for power tools are used in applications that require a lithium ion capacitor without chemical reactions at the electrodes, a capacitor such as an electric double layer capacitor has been developed.

Since activated carbon has a large surface area, but is suitably used as an electrode active material for electrochemical devices such as lithium ion capacitor using an electric double layer formed at an interface of the electrode and the electrolyte, the large surface area Therefore since to attach the activated carbon to the collector must be used binder (binder) in a large amount, as a result, a problem that the resulting electrode becomes as high internal resistance is caused, is strong binding force binders are sought in order to solve this problem.

Moreover, the binder resin used as a binder in the electrode, the oxidizing atmosphere if the electrode is used as a positive electrode, since the case used as the negative electrode is exposed long-term to a reducing atmosphere, a sufficient electrochemical stability it is necessary to have. From this viewpoint, the binder used in the fabrication of electrodes, in general, electrochemically stable polytetrafluoroethylene or fluorocarbon resins such as polyvinylidene fluoride is used.

However, the electrode made using these fluorine resins, for binding properties due to the fluororesin is not sufficient, the electrode active material from the current collector constituting the electrode fall off, there is a problem that .

To solve the problem of separation of the electrode active material, as a binder resin, for example, a component 10 to 55 mass% derived from the conjugated diene compound, the use of those containing components derived from a monofunctional aromatic vinyl compound It has been proposed (see Patent Document 1.).

However, the binder disclosed in Patent Document 1 does not have sufficient electrochemical stability, there is a problem that.

Further, for example, be higher capacity is very important the capacitor has been studied. As means corresponding to the high capacity of the capacitor, the thickness layer of the electrode layer is known to be effective, in achieving a thicker electrode layer, the slurry is good for forming an electrode it is necessary to have a coating and leveling properties.
However, when the slurry is to be applied as water-based, the surface energy of the water can not be obtained a sufficient leveling properties due to the high, in some cases such as cissing occurs, it is difficult uniform coating. In order to solve such a problem, typically, we shall have an appropriate viscosity of the slurry by using a carboxymethyl cellulose (CMC), which method of obtaining a high leveling property by is employed.

However, the conventional electrode forming composition, a low adhesion to the current collector constituting the electrode can not be obtained slurry high leveling property can be obtained, there is a problem that.

JP 2005-64294 JP

The present invention was made in view of the circumstances described above, and its object is good leveling can be obtained. Moreover capable of forming an excellent electrode layer adhesion to the current collector It is to provide an electrode-forming composition.

Another object of the present invention is to provide the electrode forming slurry according to the above composition, the electrodes and electrochemical devices.

The present inventors have studied intensively, in the composition for forming an electrode, along with a binder resin, by Ruru contain a modifying polymer consisting of polymer having a sulfonic acid (salt) group, the slurry in improving coatability and leveling property, and found that it is possible to form the electrode layer adhesion is excellent with the current collector, in which the present invention has been completed.

Electrode-forming composition of the present invention is characterized and modifying polymers, to include the (B) binder resin (A) having a sulfonic acid (salt) groups.
Here, it is preferred that the amount of the (B) the relative 100 parts by mass of the binder resin (A) modifying polymer is from 1 to 50 parts by weight.
Further, it is preferable polymer forming the (A) modifying polymer is a copolymer having a block structure.

In the present invention, the polymer (A) to form a modifying polymer, it is preferable that obtained by polymerizing a monomer having a sulfonic acid (salt) groups.
Then, the polymer forming the (A) modifying polymer,
(A) a monomer having a sulfonic acid (salt) group, and,
Monomer (b) having an acid (salt) groups, according to at least one monomer selected from the group of monomers having a skeleton derived from a monomer and an ethylene oxide or propylene oxide having a hydroxyl group it is preferably a copolymer.

In the above, the (A) modifying polymer contains a component due to a monomer having a carboxylic acid (salt) group, it is preferable that the content ratio is less than 20 mol%.
Further, the monomer having a (a) sulfonic acid (salt) group is preferably a polyisoprene sulfonic acid (salt) or (meth) acrylamido-2-methylpropane sulfonic acid (salt).
Further, the monomer having a carboxylic acid (salt) group is preferably a itaconic acid (salt).

Electrode forming slurry of the present invention, the electrode forming composition, characterized in that it comprises (C) a dispersant and (D) an electrode active material.
The electrode of the present invention is characterized by having the electrode layer formed by the above electrode forming slurry on at least one surface of the current collector.
Electrochemical device of the present invention is characterized by comprising comprises the above electrode.

According to the electrode-forming composition of the present invention, excellent leveling property and good coatability to the slurry by the composition can be obtained. Moreover it is possible to form an excellent electrode layer adhesion to the current collector .

1. Electrode forming composition for electrode formation composition of the present invention (hereinafter, simply referred to as "electrode-forming composition".) It is, modifying polymer consisting of polymer (A) having a sulfonic acid (salt) group (hereinafter, also referred to as "component (a)".) and is intended to contain and (B) a binder resin (hereinafter, also referred to as "component (B)".), usually, (C) a dispersion medium to a composition containing these components (a) and component (B).
The detail will be described below.

[1] In (A) modifying polymer present invention, the modifying polymer is a polymer having a sulfonic acid (salt) groups.
[1-1] (A) component of the production method 1
Is the component modifying polymer electrode forming composition of the present invention is a polymer having a sulfonic acid (salt) group, the sulfonic acid (salt) group-containing polymer, for example, diene structure or aromatic a base polymer containing a group structure as a precursor, sulfonated after method sulfonating part or all of the aromatic rings or residual double bonds of the precursor or some or all of the diene structure, hydrogenated the method can be obtained. For hydrogenation, can be a known hydrogenation catalyst, for example, it can be used hydrogenation catalysts and hydrogenation method described in JP-A-5-222115. After hydrogenating the base polymer, may also be sulfonated by a method described later, there is no problem even if a method of adding hydrogen after sulfonating the base polymer.

[1-1-1] Base Polymer The base polymer, be random-type, or a copolymer of a block type, such as AB type or ABA type can be used without particular limitation. As a base polymer, by using the copolymer block type, a copolymer having a sulfonic acid (salt) group having a block structure. For example, a styrene - if isoprene diblock copolymer, by using a later-described sulfuric anhydride / electron-donating compound, can be preferentially sulfonated isoprene units and styrene - isoprene block copolymerization after hydrogenation of isoprene units combined by preferentially sulfonation of the aromatic ring of the styrene by sulfuric anhydride, a copolymer having a sulfonic acid (salt) group block and a hydrophobic block can be obtained.
Preferred base polymers, such as polystyrene, isoprene homopolymer, butadiene homopolymer, a styrene - isoprene random copolymer, styrene - isoprene block copolymer, styrene - isoprene - styrene triblock copolymer, butadiene - styrene random copolymer, butadiene - styrene block copolymer, styrene - butadiene - styrene block copolymer, and hydrogenated products of these polymers, ethylene - propylene - although diene ternary copolymers, more preferably what the polymer by means of an aromatic monomer, an aromatic monomer - is a conjugated diene block copolymer, further preferred are polystyrene, a styrene - isoprene random copolymer, styrene - isoprene block copolymer and their water It is an additive.

[1-1-2] Base polymer acid to form a modified polymer of the sulfonation present invention (salt) polymer having a group, the base polymer, a known method, for example, Chemical Society of Japan edited, new experimental course (vol. 14 III, p. 1773), or by sulfonating by the method described such as in Japanese Patent Laid-Open 2-227403 discloses obtained.

That is, the base polymer, the double bond moiety in the polymer is sulfonated by a sulfonating agent. This sulfonation, double bonds or become single bond by ring-opening, or while the double bonds remaining, becomes having a hydrogen atom replaced with a sulfonic acid group. If another monomer is used, the double bond portion other than the diene unit portion, such as an aromatic unit is not problem be sulfonated. The sulfonating agent, preferably complex of sulfuric anhydride and an electron-donating compound sulfuric anhydride, sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, bisulfite (Na salt, K salt, such as Li salts) and the use .

Examples of the electron donor compound, N, N- dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, ethers such as diethyl ether; pyridine, piperazine, trimethylamine, triethylamine, amines such as tributylamine; dimethyl sulfide, diethyl sulfide sulfides such as; acetonitrile, ethyl nitrile, include such nitrile compounds such as propyl nitrile, N in these, N- dimethylformamide, dioxane is preferred.

The amount of sulfonating agent relative to the diene unit 1 mole of the base polymer, usually 0.2 to 2.0 moles sulfuric anhydrous basis, preferably 0.3 to 1.2 moles, zero. is less than 2 moles, hardly acid polymer was obtained the intended, while when it exceeds 2.0 mol, the more the residual sulfonating agent quantity such as sulfuric anhydride unreacted sulfuric acid was neutralized with an alkali salt large amount occurs, the purity of the product is reduced, which is undesirable.

In this sulfonation, it can also be used a solvent inert to the sulfonating agent such as sulfuric anhydride, as the solvent, for example chloroform, dichloroethane, tetrachloroethane, tetrachlorethylene, halogenated hydrocarbons such as dichloromethane; nitromethane, nitro compounds such as nitrobenzene; liquid sulfur dioxide, propane, butane, pentane, hexane, aliphatic hydrocarbons such as cyclohexane. These solvents can be appropriately used in combination of two or more.

The reaction temperature of this sulfonation, usually, -70 ~ + 200 ° C., preferably -30 ~ + 50 ° C., not economical slower sulfonation reaction is less than -70 ° C., whereas, in excess of + 200 ° C. Vice reaction takes place, because the product is sometimes blackened or insoluble, is not preferred.
In this way, intermediates sulfonating agent bound such as sulfuric anhydride-based polymer (sulfonic acid ester-based polymer, hereinafter referred to as "intermediates".) Is produced.

Polymer having a sulfonic acid (salt) group to form a modified polymer of the present invention, by the action of water or a basic substance to the intermediate sulfonic acid groups by ring-opening a double bond or bound becomes a single bond, or leave the double bonds remaining, obtained by hydrogen atoms replaced with a sulfonic acid group.

As the basic substance, sodium hydroxide, potassium hydroxide, alkali metal hydroxides such as lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium -t- butoxide, potassium -t- butoxide alkali metal alkoxides; sodium carbonate, potassium carbonate, carbonates such as lithium carbonate; methyl lithium, ethyl lithium, n- butyl lithium, sec- butyl lithium, amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium bromide, propyl magnesium iodide, diethyl magnesium, diethyl zinc, triethyl aluminum, organometallic compounds such as triisobutylaluminum, aqueous ammonia, trimethylamine, triethylamine Include sodium, lithium, potassium, calcium, metals such as zinc; tripropylamine, tributylamine, pyridine, aniline, amines such as piperazine.
These basic substances may also be used alone, it may be used in combination of two or more. Among these basic substances, alkali metal hydroxides, ammonia water preferred, sodium hydroxide, lithium hydroxide is preferred.

The amount of the basic substance, relative to the sulfonating agent to 1 mole used, 2 moles or less, preferably 1.3 mol or less, when more than 2 moles, the number of basic substances unreacted products purity of undesirably reduced. At the time of reaction intermediates and basic substances, it can also be used in the form of an aqueous solution of the basic substance, or the basic substance is dissolved in an inert organic solvent can be used. As the organic solvent, the various other organic solvents, benzene, toluene, aromatic hydrocarbon compounds such as xylene; methanol, ethanol, propanol, isopropanol, and alcohols such as ethylene glycol. These solvents can be appropriately used in combination of two or more.

When using a basic substance as an aqueous solution or an organic solvent solution, the concentration of the basic substance is usually 1 to 70 wt%, preferably about 10 to 50 wt%. Further, the reaction of the basic material, usually, -30 ~ + 0.99 ° C., preferably at a temperature of 0 ~ + 120 ° C., more preferably from + 50 ~ + 100 ℃, also normal pressure, either under reduced pressure or under pressure it can be carried out. Furthermore, the reaction time is usually 0.1 to 24 hours, preferably 0.5 to 5 hours.

[1-2] (A) component of the manufacturing method 2
Polymer having a sulfonic acid (salt) group to form a modified polymer of the present invention, in addition to the above method, the monomer having a sulfonic acid (salt) group (hereinafter, both "specific monomer" I say.), and, if necessary, by polymerizing a monomer component comprising a specific monomer and another monomer can be obtained.

[1-2-1] The specific monomers specific monomer, such as isoprene sulfonic acid, (meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, allyl acid, iso-amylene sulfonic acids, unsaturated (meth) allyl ether monomer represented by the following general formula (1) [for example, 3-allyloxy-2-hydroxypropane sulfonic acid, 3- Metaarirokishi 2- hydroxypropane sulfonic acid]

Figure JPOXMLDOC01-appb-C000001

Wherein, R 1 represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 8, a ~ d individually represent an integer of 0 or 1 to 100 (which is but a + b + c + d = 0 ~ 100.), (OC the 2 H 4) units and (OC 3 H 6) units are bonded in any order, Y and Z are a sulfonic acid group or a hydroxyl group, at least one of Y and Z is a sulfonic acid group. ], Sulfoethyl (meth) acrylate, the following general formula conjugated diene sulfonic acid represented by (2) (e.g., 2-methyl-1,3-butadiene-1-sulfonic acid)

Figure JPOXMLDOC01-appb-C000002
(Wherein, R 2 ~ R 7 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or -SO 3 X 6 to 20 carbon atoms (wherein X is a hydrogen atom, a metal atom, an ammonium group or an amino group.), at least one of R 2 ~ R 7 is -SO 3 X),

(Meth) acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, and salts thereof, and the like. Preferably, isoprene sulfonic acid, a (meth) acrylamido-2-methylpropanesulfonic acid, and salts thereof. Particularly preferably, isoprene sulfonic acid, a (meth) acrylamido-2-methylpropanesulfonic acid, and salts thereof.
These sulfonic acid (salt) group-containing monomers can be used also, or as a mixture of two or more used alone. The proportion of the monomer component having a sulfonic acid (salt) groups 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.

[1-2-2] polymer having a sulfonic acid (salt) group to form a modified polymer of the monomers present invention other than the specific monomers, together with the specific monomer, a carboxylic acid (salt ) monomer having a group, be those monomers having a hydroxyl group, and that at least one monomer selected from the group of a monomer having a skeleton derived from ethylene oxide or propylene oxide copolymerized it may be.

Examples of 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 carboxylic acid groups, for example, itaconic acid, itaconic anhydride, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, citraconic anhydride, glutaconic acid, vinyl acetate, allyl acetate, phosphinothricin carboxylic acid, alpha-halo acrylic acid, beta-carboxylic acid, or, these salts, (meth) acrylate, (meth) acrylate, (meth) (meth) acrylic acid alkyl esters such as octyl acrylate, and the like, preferably, itaconic acid, itaconic anhydride, acrylic acid, methacrylic acid or salts thereof. The monomer having a polymerizable double bond include those carboxylic acid (salt) groups may also be used also, or as a mixture of two or more used alone.

The monomer having a hydroxyl group, e.g., vinyl alcohol, allyl alcohol, unsaturated alcohols such as 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 mono Meth) acrylate, hydroxyl group-containing such as hydroxypropyl phenoxyethyl (meth) acrylate (meth) acrylic acid esters. Preferably, a hydroxyethyl (meth) acrylate.

Examples of the monomer having a skeleton derived from ethylene oxide or propylene oxide, polyoxyethylene monomethacrylate (alkylene oxide 1-10 mole adduct), and a compound having a structure represented by the following general formula (3)

Figure JPOXMLDOC01-appb-C000003
(Wherein, 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, a tetramethylene group.) And and the like. Among these, preferred are polyoxyethylene monomethacrylate (ethylene oxide 5 mol adduct).
The above monomers may be used alone or in combination.

Polymer having a sulfonic acid (salt) group to form a modified polymer of the present invention may also be in addition to the above monomer components, obtained by copolymerizing other copolymerizable monomers . Such other monomer, styrene, alpha-methyl styrene, vinyl toluene, aromatic vinyl compounds such as p- methylstyrene, butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3 - aliphatic conjugated dienes such as butadiene, and the like vinyl cyanide compounds such as (meth) acrylonitrile. These monomers may be used alone or in combination. In the case of copolymerizing these other monomers is preferably not more than 30 mol% in the total monomers.

In the present invention, (A) Preferred examples of the modifying polymer components, certain homopolymer of a monomer, the particular monomer and the carboxylic acid (salt) monomer having a group and by the copolymer , and the like copolymers according the monomer having a monomer and a hydroxyl group having a specific monomer and a carboxylic acid (salt) groups. In the copolymer according to the monomer having a specific monomer and a carboxylic acid (salt) group, the content of the component by a monomer having a carboxylic acid (salt) group is preferably less than 90 mol%, more preferably 85 to 5 mol%, particularly preferably 80 to 10 mol%.

[1-2-3] Among the methods for obtaining a polymer having a sulfonic acid (salt) group are reforming polymer in the polymerization the present invention of the monomer component, the particular monomer (sulfonic acid ( manufacturing method using a monomer composition containing a monomer) with a salt) group, for example, as follows.
That is, a composition according to the monomer component, hydrogen peroxide, sodium persulfate, the presence of a known polymerization initiator such as potassium persulfate, usual reaction temperature 20 ~ 200 ° C., preferably at 40 ~ 0.99 ° C. the reaction time of 0.1 to 20 hours, preferably by polymerization reaction for 1 to 15 hours, it is possible to produce the desired polymer. In some instances, a monomer component used for polymerization successively added, it is possible to carry out the polymerization. Here, the "sequential polymerization", a constant amount per unit time, or the amount of the by-variate added, there polymerization process to introduce within a predetermined time the monomer component to the polymerization system.

In this polymerization reaction, a polymerization solvent for conducting the reaction smoothly can be used. As the polymerization solvent, water or a mixture of water-miscible organic solvent and water, or the like can be used. The Examples of the organic solvent is not particularly limited as long as it can mix with water, such as tetrahydrofuran, 1,4-dioxane, and alcohols.

[1-3] The weight-average molecular weight of the polymer having the sulfonic acid (salt) group to form a modifying polymer having a molecular weight present invention of the component (A) is 1,000 to 500,000, preferably from 3 000 to 300,000, and more preferably from 5,000 to 300,000. Having a weight average molecular weight exceeds 500,000, is accompanied and gelation usually becomes difficult to handle.

[1-4] modifying polymer of the component (A) of the sulfonate present invention may be a polymer having a cationic species counter ions other than hydrogen. Cationic species include, but are not limited to, alkali metals, alkaline earth metals, ammonium, amines are preferred. Examples of the alkali metal include sodium, potassium and the like, calcium as an alkaline earth metal, magnesium, and the like, the amine methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, such as tributylamine alkylamines, ethylenediamine, diethylenetriamine, polyamines such as triethylenetetramine can be exemplified morpholine, piperidine and the like. Preferably, potassium, ammonium, alkyl amine.
To obtain a polymer (salt) having these cationic species may be by polymerizing a monomer having the preferred cationic species, after copolymerizing a monomer of acid type, medium in the appropriate alkali it may be sum. It is also possible to interchangeable with other types of cationic species by polymer (salt) of various ion-exchange techniques. These, the cations may be used alone, it can be used in combination of two or more.

In [1-5] (A) electrode forming composition content present invention component, modifying polymer of the component (A) to (B) described later 100 mass parts of the binder resin, usually 1 to 50 parts by weight, it is used in amounts preferably comprised between 2 and 50 parts by weight, particularly preferably from 3 to 40 parts by weight. By the content of the modifying polymer is within the above range, can be excellent in adhesion to the current collector constituting the electrode, providing a good slurry film thickness uniformity is obtained by good leveling properties it is possible to provide an electrode-forming composition. If the content of the component (A) is too small, the slurry leveling property is deteriorated, there is a tendency that adhesion of the resulting electrode layer is deteriorated. On the other hand, when the content of the component (A) is excessive, even leveling property is a good, tends to the relative proportions of the binder resin can not be obtained sufficient adhesion to decrease.

[2] (B) a binder resin (B) component is a binder resin, a component which acts as a binder. As the component (B), can be adopted for use in the general cell electrode binder and a capacitor electrode binder and the like. (B) Examples of the suitable component, styrene-butadiene-based polymer, and (meth) acrylic polymer, a composite product of a fluorine-based polymer and a fluorine-based polymer (meth) acrylic polymer or the like . Incidentally, these binder resins may be used in combination either singly or in combination.

Styrene-butadiene-based polymer is a polymer having a structural unit derived from a structural unit and a conjugated diene compound derived from an aromatic vinyl compound as essential constituent units. Further, (meth) acrylic polymer is a polymer having as essential constituent units at least one of constitutional units derived from the structural units and methacrylic acid esters derived from acrylic acid ester. Further, fluorine-based polymer is a polymer having polymerizable compound containing a fluorine atom a structural unit derived from a (fluorine-based monomer) as essential constituent units.

The term "(meth) - acrylic acid" as used herein, means any "acrylic acid ..." and "methacrylic acid ...". Also, the term "- (meth) acrylate" refers to any "- acrylate" and "- methacrylate".

Component (B), a conjugated diene compound, aromatic vinyl compound, a polymer having a structural unit derived from (meth) acrylate compound, a polymerizable monomer of ethylenically unsaturated compounds and the like fluorine-based monomer It is preferred. Note that these polymerizable monomers may be used in combination either singly or in combination.

[2-1] Examples of the conjugated diene compound-conjugated diene compound, 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, may be mentioned chloroprene. Of these, 1,3-butadiene is preferable. These conjugated diene compounds may be used in combination either singly or in combination.

Specific examples of [2-2] an aromatic vinyl compound-aromatic vinyl compound, styrene, alpha-methyl styrene, p- methyl styrene, vinyl toluene, chlorostyrene, can be mentioned divinylbenzene and the like. Of these, styrene is preferred. These aromatic vinyl compounds may be used in combination either singly or in combination.

[2-3] Specific examples of the (meth) acrylate compound (meth) acrylate compounds are 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 , mention may be made of i- nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate. Of these, methyl (meth) acrylate, n- butyl (meth) acrylate, i- butyl (meth) acrylate are preferable, methyl (meth) acrylate is more preferable. These (meth) acrylate compounds may be used in combination either singly or in combination.

[2-4] Examples of ethylenically unsaturated carboxylic acids ethylenically unsaturated carboxylic acids include (meth) acrylic acid, itaconic acid and the like.

[2-5] Examples of the fluorine-based monomer fluorine-based monomers, vinylidene fluoride, hexafluoropropylene, vinyl fluoride, tetrafluoroethylene, perfluoroalkyl vinyl ethers, fluoroalkyl (meth) acrylate it can be mentioned. Among these, vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, fluoroalkyl (meth) acrylate. These fluorine-based monomers may be used in combination either singly or in combination.

The often oxidation resistance is required the electrode, in order to meet this requirement, as the binder resin, it is effective to use a structural unit derived from a fluorine-based monomer is introduced polymer . Particularly, in the present invention, it is preferable to use a fluorine-based polymer and a (meth) composite compound of the acrylic polymer.

[2-6] The monomer composition which is a raw material for producing other monomer component (B), a monomer other than the polymerizable monomers described above, the above-mentioned polymerizable monomer copolymerizable with those (hereinafter, referred to as "copolymerizable compound".) may be contained.

Specific examples of the copolymerizable compound, (meth) acrylamides, alkyl amides of ethylenically unsaturated carboxylic acids such as N- methylolacrylamide, vinyl acetate, vinyl carboxylate vinyl propionate; ethylenically unsaturated dicarboxylic acids acid anhydride, monoalkyl esters or monoamides; aminoethyl acrylamide, dimethylaminoethyl methacrylamide, an aminoalkyl amides of ethylenically unsaturated carboxylic acids such as methyl amino propyl methacrylamide; (meth) acrylonitrile, etc. α- chloro acrylonitrile vinyl cyanide compounds, and the like. These copolymerizable compounds can be used in combination either singly or in combination.

[2-7] In the case of using a styrene-butadiene-based polymer as styrene-butadiene-based polymer component (B), the proportion of the conjugated diene compound contained in the monomer composition to be 20 to 58 wt% preferably, further preferably 30 to 55 mass%. If the content of the conjugated diene compound is less than 20 wt%, the resulting copolymer becomes higher glass transition temperature, flexibility of the electrode layer and that is formed, the adhesion of the electrode layer to the current collector decreases They tend to be. On the other hand, the content of the conjugated diene compound is more than 58 mass%, since the surface of the electrode layer to be formed tends to gradually showing tackiness, etc. electrode layers during press working will stick to the rolls, processed gender tends to decrease.

The proportion of the aromatic vinyl compound contained in the monomer composition is preferably from 10 to 55 wt%, more preferably 20 to 50 mass%. If the content of the aromatic vinyl compound is less than 20 wt%, for example, will be reduced interaction with graphite used as an electrode active material, graphite from the electrode layer to be formed is in the easily tends to fall off . On the other hand, the content of the aromatic vinyl compound exceeds 55 mass%, tends to become brittle resulting polymer is stiff ones, the flexibility of the electrode layer and that is formed, the adhesion of the electrode layer to the current collector decreases They tend to be.

The polymer is a binder resin may include a component due to a monomer other than the conjugated diene compound and an aromatic vinyl compound. Examples of such a monomer include a (meth) acrylate compounds and ethylenically unsaturated carboxylic acid. The proportion of the (meth) acrylate compound containing a monomer composition is preferably 5 to 30 mass%, more preferably 10 to 25 mass%. When a (meth) in proportion is less than 5 wt% of acrylate compound tends to easily binder becomes low affinity for the electrolyte of the resulting polymer becomes electric resistance component, the internal resistance of the battery is increased . On the other hand, (meth) If the content of the acrylate compound is more than 25 mass%, it is as the resulting polymer is excessively absorbed electrolyte tends to disappear binding property in the battery, deterioration of the battery during high temperature storage there is a tendency that is likely to occur.

The proportion of the ethylenically unsaturated carboxylic acid contained in the monomer composition for obtaining the binder resin, more preferably preferably from 0.5 to 6 wt%, 1-5 wt% . If the content of the ethylenically unsaturated carboxylic acid is less than 0.5 wt%, in preparing the electrode forming composition, dispersion stability is insufficient particles comprising a polymer (polymer particles), aggregates there is a tendency that is likely to occur. Therefore, there is a tendency that the adhesion of the electrode layer to the current collector tends to occur problems such as decrease. On the other hand, the content of the ethylenically unsaturated carboxylic acid is more than 6 wt%, the viscosity of the prepared electrode-forming composition ends up over time rises during storage, the coating tends to decline.

[2-8] In the case of using (meth) acrylic polymer as the component (B) of (meth) acrylic polymer, the proportion of the (meth) acrylate compound containing a monomer composition, 50 to 100 it is preferably mass%, and further preferably from 70 to 100 mass%. (Meth) If the content of the acrylic polymer is less than 50 wt%, liable to lack flexibility of the electrode (electrode plate), there is a crack will enter.

Further, (meth) acrylic polymer may include a component due to a monomer other than the above (meth) acrylate compound. Such monomers, and aromatic vinyl compounds and vinyl cyanide compounds. The proportion of the aromatic vinyl compound contained in the monomer composition is preferably 0 to 20 mass%, more preferably 0-10 wt%. If the content of the aromatic vinyl compound is more than 20 mass%, the flexibility of the resulting electrode (electrode plate) it is likely insufficient, resulting in cracked.

The proportion of the vinyl cyanide contained in the monomer composition to obtain a resin binder for is preferably 0 to 30 mass%, more preferably 0 to 20 mass%. If the content of the vinyl cyanide exceeds 30 mass%, tends to lack the flexibility of the electrode (electrode plate), there is a crack will enter.
The proportion of ethylenically unsaturated carboxylic acid contained in the monomer composition, preferably 0.5 to 6% by weight, and more preferably 1 to 5 mass%. If the content of the ethylenically unsaturated carboxylic acid is less than 0.5 wt%, in preparing the electrode forming composition, dispersion stability is insufficient particles comprising a polymer (polymer particles), aggregates in the easy tends to occur. On the other hand, the content of the ethylenically unsaturated carboxylic acid is more than 6% by mass, the viscosity of the prepared electrode-forming composition is increased over time under storage process, there is a tendency that coatability is lowered .

[2-9] In the case of using a fluorine-based polymer as the fluorine-based polymer component (B), the proportion of vinylidene fluoride contained in the monomer composition is preferably 85 to 100 mass%. If the content of vinylidene fluoride is less than 85 mass%, there is a case where adhesion of the electrode layer to the current collector is lowered, there is a tendency that the electrode layer is liable to peel.

Further, fluorine-based polymer may include tetrafluoroethylene in the monomer composition. Ratio of tetrafluoroethylene to be contained in the monomer composition is preferably 0 to 5 mass%. If the content of tetrafluoroethylene is more than 5 mass%, tends to lack the flexibility of the electrode (electrode plate), there is a crack will enter. The proportion of hexafluoropropylene is contained in the monomer composition is preferably 0 to 10 mass%. If the content of hexafluoropropylene is more than 10 mass%, there is a case where adhesion of the electrode layer to the current collector is lowered, there is a tendency that the electrode layer is liable to peel.
Furthermore, the fluorine-based polymer may comprise a component due to a monomer other than the fluorine-based monomer in the monomer composition.
Further, as described in JP-A-3-7784, the resulting fluorine-based polymer by polymerizing the (meth) acrylate compound as a seed, a fluorine-based polymer (meth) acrylic polymer preferably a composite compound as the component (B).

[2-10] The polymer particles (B) component binder resins to form polymeric particles, it is preferably contained in the electrode-forming composition in the form of a latex. The number average particle diameter of the polymer particles contained in the latex is preferably from 70 ~ 350 nm, further preferably 80 ~ 300 nm. If the number average particle diameter of the polymer particles is within the above range, the movement at the time of drying the coating layer made of the electrode-forming composition coated on the surface of the current collector, the polymer particles to the surface of the coating layer without the surface of the formed electrode layer is preferable because less likely to sticky. Therefore, the electrode layer is less likely to be peeled off during the press working. Furthermore, also preferable in terms of adhesion of the electrode layer to the current collector is not reduced.

[2-11] The glass transition temperature (Tg) of
(B) a glass transition temperature of the binder resin constituting the component (Tg) of preferably from -40 ~ 50 ° C., further preferably -35 ~ 30 ° C.. The glass transition temperature of the binder resin by in the above range, be sticky excessive increase of the electrode plate surface is suppressed. Therefore, sticking to rolls does not easily occur during pressing, since the separation of the resulting electrode layer can be suppressed, which is preferable. Furthermore, the securing flexibility of the electrode layer to be formed, in that the cracks are hardly generated in the electrode layer, preferably.

[3] (C) dispersant electrode-forming composition of the present invention typically has (A), (B) component and the "other components" which are blended if necessary is the component (C) in which is dispersed in the dispersion medium. As the dispersion medium may be water. As described above, when contained in the electrode-forming composition in a latex state to form a component (B) polymer particles, the latex can be prepared by emulsion polymerization. Therefore, were used during the emulsion polymerization of water as (C) can be a dispersion medium for component, or a material obtained by concentrating the water used during the emulsion polymerization can also be directly as a dispersion medium.

On the other hand, water as a dispersion medium, may be replaced with a suitable organic dispersion medium in the electrode active material as needed. Examples of the organic dispersion medium, for example, aromatic hydrocarbon compounds, aromatic hydrocarbon compounds, chlorine-containing hydrocarbon compounds, nitrogen-containing hydrocarbon compounds, can be used sulfur-containing hydrocarbon compounds and the like. Specific examples of the organic dispersion medium, toluene, N- methylpyrrolidone (NMP), methyl isobutyl ketone (MIBK), cyclohexanone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) or the like.

Method of replacing the organic dispersion medium of water is not particularly limited, for example,
(1) adding an organic dispersion medium in latex prepared by emulsion polymerization, a method of evaporating the water by distillation under reduced pressure,
(2) the water from the latex is evaporated, the method redispersing solids obtained organic dispersion medium and the like are preferable.

[4] (D) (D) component in the electrode active material present invention is an electrode active material. For example, in the electrode forming composition used to manufacture an electric double layer capacitor electrode, specific examples of the electrode active material, it may be mentioned activated carbon, activated carbon fiber, silica, alumina, or the like. Furthermore, the electrode forming composition used to manufacture the lithium ion capacitor electrode, specific examples of the electrode active material, graphite, non-graphitizable carbon, hard carbon, carbon materials such as coke, polyacene-based organic semiconductor (PAS ), and the like.

Contained in the electrode-forming composition of the present invention, the total amount of components (A) and component (B) is preferably 0.1 to 10 parts by mass with respect to 100 parts by weight of component (D), is preferably 0.3 to 4 parts by mass. By total content of solids of component (A) and component (B) is in the above range, as high adhesion to the current collector, it does not adversely affect the electrical characteristics of the electrochemical device to be produced preferable from the point of view of.

[5] The method of preparing the preparation electrode forming composition of the electrode-forming composition is not particularly limited. For example components (A) to the component (D), by mixing the additive to be optionally added (Other components), it can be prepared. Specifically, for example, advance (D) advance the component (B) mixture is added to the ingredients to prepare a method for mixing the mixture with the component (A), or with respect to component (D) (A ) by adding components and component (B), can be prepared electrode-forming composition.
The mixing of the components, can be used a stirrer, defoaming machine, a bead mill, a high-pressure homogenizer or the like. The mixing is preferably carried out under reduced pressure. By mixing the components under reduced pressure, it is possible to prevent the bubbles generated in the electrode layer formed by using the used electrode-forming composition obtained.

(B) in the case to be manufactured in advance (D) component was added the mixture components, solid concentration of the mixture, it is preferably from 20 to 53 wt%, 25 to 50 mass% A further preferred. When the solid concentration exceeds 53 mass%, in the viscosity of the mixture becomes high, sometimes handled in the formulation process of weighing the like becomes difficult. On the other hand, if the solid concentration is less than 20 wt%, the content of solids in the electrode-forming composition obtained is lowered, it is difficult to form an electrode layer having a desired thickness .

Suitable solid concentration of the electrode forming composition is generally depends on the type of electrode to be produced. For example, the electrode forming composition, when used as a negative electrode-forming slurry for a lithium ion battery electrode is preferably solid concentration in the electrode-forming composition is 30 to 60 mass%. Furthermore, the electrode forming composition, when used as a slurry capacitor electrode is preferably solid concentration of the capacitor electrode composition is 20 to 40 mass%. Here, the "solids" refers to the components excluding the dispersion medium from all components contained in the electrode-forming composition.

2. Electrodes of the electrode present invention, a current collector, the foregoing electrode-forming composition on the surface of the current collector is applied, an electrode layer formed is dried, in which with a.
Electrode layer of the electrode of the present invention are those which are formed by using the above electrode forming composition. Thus, the electrode of the present invention, the adhesion strength between the current collector and the electrode layer is high, and has a property of having excellent thickness uniformity.

[1] As the current collector current collector, it is possible to use a metal foil, etching the metal foil, expanded metal or the like. As the material constituting the current collector, for example, can be cited aluminum, copper, nickel, tantalum, stainless steel, a metal material such as titanium.
Incidentally, depending on the type of electrochemical device to be produced, may be selected as appropriate from these metallic materials. For even thickness of the current collector may be appropriately set according to the type of electrochemical device to be produced. For example, in the case of producing an electrode for an electric double layer capacitor, the thickness of the electrode layer is preferably in the 5 ~ 100 [mu] m, more preferably be 10 ~ 70 [mu] m, particularly preferably in the 15 ~ 30 [mu] m.

[2] electrode layer electrode layer is formed by forming a coated layer by applying the above-mentioned electrode-forming composition on the surface of the current collector (coating layer) can be formed by drying. After drying the coating layer may be pressing as necessary.

Specific examples of the method of applying the electrode-forming composition on the surface of the current collector, doctor blade method, a reverse roll method, comma bar method, gravure method, an air knife method. Temperature for drying the coated film is preferably from 20 ~ 250 ° C., further preferably 50 ~ 0.99 ° C.. The drying time of the coating layer is preferably in the for 1 to 120 minutes and more preferably be between 5-60 minutes.

In the case of pressing after drying the coating layer, this pressing can be used high-pressure super-press, soft calender, a machine of such as one ton press machine. Conditions of pressing is appropriately set in accordance with the processing machine to be used. The thickness of the thus electrode layer formed is usually 40 ~ 100 [mu] m. The density of the electrode layer is generally from 1.3 ~ 2.0g / cm 2.

3. Electrochemical devices of the electrochemical device The present invention having the above-mentioned electrode. Namely, the electrochemical device of the present invention has high adhesion strength between the current collector and the electrode layer, since those having a high leveling property of the electrode layer electrode, those having a high degree of product reliability.

Examples of electrochemical devices can include an electric double layer capacitor, a capacitor such as a lithium ion capacitor, lithium ion secondary battery, a secondary battery such as a nickel-hydrogen secondary battery, the others.

In addition, when the electrochemical device is a lithium ion capacitor, as an electrolytic solution, for example, the electrolytic solution used was a lithium compound as an electrolyte dissolved in a solvent. Specific examples of 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, LiC 4 F 9 SO 3, Li (C 4 F 3 SO 2) 2 N, Li [CO 2) 2] 2 B and the like.

Specific examples of the solvent of the electrolytic solution, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, carbonates such as methyl ethyl carbonate; lactones such as γ- butyrolactone; trimethoxysilane, 1,2- ethane, diethyl ether, 2-ethoxy ethane, ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; 1,3-dioxolane, oxolane such as 4-methyl-1,3-dioxolane; acetonitrile, nitrogen-containing compounds such as nitromethane; methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, and phosphoric acid triesters; diglyme, triglyme, Te Glymes such Raguraimu; oxazolidinones such as 2-methyl-2-oxazolidinone; sulfones such as sulfolane; acetone, diethyl ketone, methyl ethyl ketone, ketones such as methyl isobutyl ketone 1,3-propane sultone, 1,4 butane sultone, mention may be made of 1,8-sultone such as Nafutasuruton like.

Capacitor when an electric double layer capacitor, an electrolytic solution of an electrolyte dissolved in the above solvent for an electric double layer capacitor is used. Specific examples of the electrolyte for an electric double layer capacitor, may be mentioned tetraethyl ammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate, and the like.

Hereinafter, the examples present invention further specifically described, the present invention is not limited to the following examples. Incidentally, "%" in the examples and "parts" are by weight unless otherwise noted. Further, various measurements in the examples were carried out as follows.

[Weight-average molecular weight]
The weight average molecular weight (Mw), in which the result of the determination by gel permeation chromatography (GPC), was converted using a calibration curve prepared with sodium polystyrenesulfonate 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]
Connect column (1) to (3) in series in this order, the sample is introduced from the column (1) side. Detector: [manufactured by Tosoh Corporation] differential refractometer RI-8021
Eluent: water / acetonitrile / sodium sulfate = 2,100 / 900/15 (weight ratio) Flow rate: 1.0 ml / min Temperature: 40 ° C.
Sample concentration: 0.2%
Sample injection volume: 400μl

[Reforming Polymer Production Example 1]
The inner volume of 2 liters was charged polystyrene 100 g, was dissolved in 1,2-dichloroethane liter. After dissolution, the anhydrous 77g sulfate, the internal temperature was dropped into the vessel while maintaining the 25 ° C., after completion of the dropwise addition, the mixture was stirred for 1 hour at 25 ° C.. Thereafter, water and to counterion addition of sodium hydroxide and (Na +), etc. to remove the solvent, to obtain a sodium salt of sulfonated polystyrene (A). The weight average molecular weight of the polymer (salt) was 10,000.

[Reforming Polymer Production Example 2]
The inner volume of 3 liters of styrene / isoprene (20/80 mole ratio) were charged random copolymer 100 g, was dissolved in dioxane liter. After dissolution, the sulfuric acid / dioxane complex anhydride (85 g / 500 g), the internal temperature was dropped into the vessel while maintaining the 25 ° C., after completion of the dropwise addition, the mixture was stirred for 1 hour at 25 ° C.. Thereafter, water and additives to counterion sodium hydroxide and (Na +), etc. to remove the solvent, styrene / isoprene (20/80 mole ratio) random copolymer sulfonated sodium salt of the (B) It was obtained. The weight average molecular weight of the copolymer (salt) was 5,000.

[Reforming Polymer Production Example 3]
The inner volume of 3 liters was charged with styrene / isoprene (30/70 mole ratio) AB type block copolymer 100 g, it was dissolved in dioxane liter. After dissolution, the sulfuric acid / dioxane complex anhydride (71 g / 500 g), was added dropwise to the vessel while maintaining the internal temperature at 25 ° C.. After completion of the dropwise addition, it stirred for 1 hour at 25 ° C., and preferentially sulfonated isoprene units. Thereafter, water and by adding counterions of sodium hydroxide and (Na +), etc. to remove the solvent, styrene / isoprene (30/70 mole ratio) AB type block copolymer (20/80 mole ratio) to obtain a sodium salt of the sulfonated product (C). The weight average molecular weight of this copolymer was 15,000.

[Reforming Polymer Production Example 4]
In a vessel having an internal volume of 2 liters of 35% aqueous hydrogen peroxide 14g was dissolved in water 100 g, 20% strength sodium styrenesulfonate aqueous 500 g, was added dropwise evenly over 2 hours with stirring under reflux. After completion of the dropwise addition, was kept under reflux for 10 hours to obtain the reaction is complete to counterion a (Na +) in a polymer (D). The weight average molecular weight of this polymer was 8,000.

[Reforming Polymer Production Example 5]
In the production example 4, a 20% strength instead of styrene sulfonic acid sodium aqueous solution 500g, except for using isoprene sulfonate aqueous sodium 500g of a 20% strength in the same manner as in Preparation Example 4, isoprene sulfonic acid polymer It was obtained sodium salt (E). The weight average molecular weight of the polymer (salt), was 15,000.

[Reforming Polymer Production Example 6]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500g, except for using a 20% strength acrylamido-2-methylpropanesulfonic acid sodium aqueous solution 500g in the same manner as in Preparation Example 4, acrylamide to give 2-methylpropanesulfonic acid sodium polymer (F). The weight average molecular weight of this polymer was 20,000.

[Reforming Polymer Production Example 7]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, except for using a 20% strength acrylamido-2-methylpropanesulfonic acid sodium aqueous solution 305 g, and the concentration of 30% itaconic acid solution 130g in the same manner as in production example 4 was obtained acrylamido-2-methylpropanesulfonic acid sodium / itaconic acid (50/50 mole ratio) copolymer (G). The weight average molecular weight of the copolymer was 8,000.

[Reforming Polymer Production Example 8]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% concentration of the isoprene sulfonic acid sodium aqueous solution 440 g, and 30% concentrations using itaconic acid aqueous solution of sodium 40 g, counterions (NH 3 +) and except were in the same manner as in production example 4, to obtain a sodium isoprene sulfonate / sodium itaconate (85/15 mole ratio) copolymer of an ammonium salt (H). The weight average molecular weight of the copolymer (salt) was 5,000.

[Reforming Polymer Production Example 9
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% concentration of acrylamide-2-methylpropanesulfonic acid sodium aqueous solution 431 g, and 20% concentrations of polyoxyethylene monomethacrylate (ethylene oxide 5 except for the use of mole adduct) solution 69g is in the same manner as in preparation example 4, to give acrylamido-2-methylpropane sulfonic acid sodium / polyoxyethylene monomethacrylate (90/10 mole ratio) copolymer (I) It was. The weight average molecular weight of this copolymer was 15,000.

[Reforming Polymer Production Example 10]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% strength acrylamido-2-methylpropanesulfonic acid sodium aqueous solution 479g, and a 20% strength aqueous solution of sodium 21g acrylic acid used, pairs except that the ions (Na +) in the same manner as in preparation example 4, was obtained acrylamido-2-methylpropane sodium sulfonate / acrylate (90/10 mole ratio) copolymer of sodium salt of (J) . The weight average molecular weight of the copolymer (salt) was 10,000.

[Reforming Polymer Production Example 11]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% strength acrylamido-2-methylpropanesulfonic acid sodium aqueous solution 64 g, and 20% concentration except for using the acrylic acid aqueous solution 7g in the same manner as in production example 4 was obtained acrylamido-2-methylpropanesulfonic acid sodium / acrylic acid (85/15 molar ratio) copolymer (K). The weight average molecular weight of this copolymer was 10,000.

[Reforming Polymer Production Example 12]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, except for using 20% ​​concentration of the isoprene sulfonic acid sodium aqueous solution 485 g, and 20% strength aqueous methacrylic acid solution 15g of Production Example 4 It was obtained in the same manner isoprene sulfonic acid sodium / methacrylic acid (95/5 mole ratio) copolymer (L). The weight average molecular weight of this copolymer was 10,000.

[Reforming Polymer Production Example 13]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% concentration of the isoprene sulfonic acid sodium aqueous solution 152 g, 20% concentration of aqueous acrylic acid solution 570 g, and a 20% strength hydroxyethyl methacrylate solution 115g except for the use of in the same manner as in preparation example 4 to obtain isoprene sulfonic acid sodium / acrylic acid / hydroxyethyl methacrylate (10/80/10 molar ratio) copolymer (M). The weight average molecular weight of the copolymer was 9,000.

[Reforming Polymer Production Example 14]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% concentration of the isoprene sulfonic acid sodium aqueous solution 443 g, 20% concentration of sodium acrylate aqueous solution 13 g, and 20% concentrations of polyoxyethylene mono methacrylate used (ethylene oxide 5 mol adduct) aqueous solution 44 g, except that the counter ion and (Na +) in the same manner as in preparation example 4, sodium isoprene sulfonate / acrylic acid / polyoxyethylene monomethacrylate (90 / 5/5 mole ratio) copolymer was obtained the sodium salt of (N). The weight average molecular weight of the copolymer (salt) was 15,000.

[Reforming Polymer Production Example 15]
In the production example 4, instead of 20% strength sodium styrenesulfonate aqueous 500 g, 20% concentration of acrylamide-2-methylpropanesulfonic acid sodium aqueous solution 373 g, and 20% concentration except for using the acrylic acid aqueous solution 127g in the same manner as in production example 4 was obtained acrylamido-2-methylpropanesulfonic acid sodium / acrylic acid (50/50 molar ratio) copolymer (O). The weight average molecular weight of this copolymer was 12,000.

[Fluoropolymer and (meth) Synthesis of the complex product of the acrylic polymer]
After the inside of the inner volume of about 6 liter autoclave equipped with an electromagnetic stirrer was fully purged with nitrogen, charged with perfluoro decanoic acid ammonium 25g as 2.5 liters of pure and emulsifier deoxygenated while stirring at 350 rpm 60 ℃ and the temperature was raised to. Then, was charged vinylidene fluoride (VDF) 44.2% and hexafluoropropylene (HFP) mixed gas consisting of 55.8%, until the internal pressure reached 20kg / cm 2 G. Thereafter, Freon 113 solution 25g containing 20% ​​of diisopropyl peroxydicarbonate as a polymerization initiator, and pressed using a nitrogen gas to initiate the polymerization reaction. During the polymerization reaction, the pressure was maintained at 20 kg / cm 2 G by sequentially pressing the mixed gas consisting of VDF60.2% and HFP39.8%. Further, since the polymerization rate with the progress of the polymerization reaction is lowered, after 3 hours had passed, and the original and the same amount of the polymerization initiator was pressed using nitrogen gas, it is further continued for 3 hours. The reaction was stopped stirred with cooling, the reaction to release unreacted monomers was thus obtained latex of a fluorine-based polymer.
After fully purged with nitrogen inside the separable flask capacitor 7 liters 150 parts latex of the fluorine-based polymer as (in terms of solid content) and emulsifier 2- (1-allyl) -4-nonylphenoxy polyethylene glycol sul were charged 3 parts phosphate of ammonium, it was heated to 75 ° C.. Next, 60 parts of n- butyl acrylate, 36 parts of methyl methacrylate, 2 parts of acrylic acid, 2 parts of itaconic acid and an appropriate amount of water was added, followed by stirring at 75 ° C. 30 min. Thereafter, 0.5 part of sodium persulfate was added as a polymerization initiator were polymerized for 2 hours at 85 ~ 95 ° C.. The cooled and quenched to obtain an aqueous dispersion of a fluorine-based polymer (meth) composite compound of the acrylic polymer (1).

Example: Preparation of an evaluation electrode]
(1) an electric double layer capacitor generally electrode (1)
Activated carbon "KURARAY COAL YP" (manufactured by Kuraray Chemical Co., Ltd.) 100 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), 6 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.) 2 parts, a fluorine-based polymer ( meth) binder resin 4 parts consisting composite compound of the acrylic polymer (1), and production example 13 by the copolymer modifying polymer, 1 part of which consists of (M), the slurry solids concentration 25% by stirring with ion-exchanged water to a, to prepare a uniform evaluation electrode forming slurry.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layer was obtained by the evaluation electrode (1) formed of.

(2) an electric double layer capacitor generally electrode (2)
Activated carbon "KURARAY COAL YP" (manufactured by Kuraray Chemical Co., Ltd.) 100 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), 4 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.) 1.5 parts Fluorine-based polymer and (meth) binder resin 4 parts consisting composite compound of the acrylic polymer (1), and a copolymer prepared according to preparation example 13 modifying polymer, 1 part of which consists of (M), the slurry solids concentration by stirring with ion-exchanged water to a 25%, to prepare a uniform evaluation electrode forming slurry.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layer for evaluation was obtained electrode formed (2) to be.

(3) (manufactured by Kuraray Chemical Co., Ltd.) a lithium ion capacitor cathode electrode activated carbon "KURARAY COAL YP" 92 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha) (manufactured by Daicel Chemical Industries, Ltd.) 6 parts of carboxymethyl cellulose 4 parts of a fluorine-based polymer (meth) binder resin 4 parts consisting composite compound of the acrylic polymer (1), and the copolymers according to preparation 13 consisting (M) modifying polymer, 1 part the slurry solids concentration by stirring with ion-exchanged water to a 25%, to prepare a uniform evaluation electrode forming slurry.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layers to obtain a formed for evaluation electrode (3).

(4) In the preparation of the evaluation electrode (4) - (17) Preparation the evaluation electrode (3) of, in place of the copolymer (M), heavy for the "modification of Table 1 as a modifier for polymer except for using those described in the column of coalescence "were obtained in the same manner for evaluation electrode (4) to (17).

Comparative Example: Preparation of an evaluation electrode]
(5) an electric double layer capacitor generally electrode 1
Activated carbon "KURARAY COAL YP" (manufactured by Kuraray Chemical Co., Ltd.) 100 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), 6 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.) 2 parts, a fluorine-based polymer ( the binder resin 5 parts consisting meth) composite compound of the acrylic polymer (1), by the slurry solids concentration is stirred with deionized water to be 25% homogeneous for evaluation electrode formed the slurry was prepared.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layer for evaluation was obtained electrode formed (18).

(6) an electric double layer capacitor generally electrode 2
Activated carbon "KURARAY COAL YP" (manufactured by Kuraray Chemical Co., Ltd.) 100 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), 4 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.) 1.5 parts Fluorine-based polymer and (meth) the binder resin 5 parts consisting composite compound of the acrylic polymer (1), by the slurry solids concentration is stirred with deionized water to be 25% homogeneous evaluation electrode the forming slurry was prepared.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layer for evaluation was obtained electrode formed (19) to be.

(7) an electric double layer capacitor generally electrode 3
Activated carbon "KURARAY COAL YP" (manufactured by Kuraray Chemical Co., Ltd.) 92 parts of conductive carbon "DENKA BLACK" (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), 6 parts of carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.) 4 parts of a fluorine-based polymer ( the binder resin 5 parts consisting meth) composite compound of the acrylic polymer (1), by the slurry solids concentration is stirred with deionized water to be 25% homogeneous for evaluation electrode formed the slurry was prepared.
This evaluation electrode forming slurry was uniformly coated by a doctor blade method on the surface of an aluminum foil having a thickness of 20 [mu] m. After drying for 15 minutes at a temperature 120 ° C. using a dryer, by further dried under reduced pressure for 2 hours at 5 mmHg, 0.99 ° C. using a vacuum dryer, to one surface of a current collector made of aluminum foil, containing activated carbon electrode layers to obtain a formed for evaluation electrode (20).

[Evaluation Experiment]
(8) Measurement of in-plane distribution of the electrode layer thickness (leveling Ratings)
For each of the evaluation electrode (1) to (17) and the evaluation electrode (18) to (20), cut width 12cm, length 12cm test pieces in the test piece, each vertical 2cm, horizontal 2cm dimension the region a total of 36 squares, the film thickness was measured using a film thickness meter (manufactured by Mitutoyo Digimatic MICROMETER IP65), and calculates the ratio (%) of the standard deviation to the mean value of the thickness thereof. The results are shown in Table 1. The higher the number of the ratio is smaller, is evaluated to be excellent in leveling property.

For each of (9) current collector and the electrode layer adhesion measured the evaluation electrode (1) to (17) and the evaluation electrode (18) to (20), a width 2 cm, the test piece of length 10cm cut, the surface of the electrode layer side of the test piece, along with the paste to an aluminum plate by means of a double-sided tape, the surface of the current collector side of the test strip, adhesive tape "Cellotape (registered trademark)" width 18 mm (manufactured by Nichiban Co., Ltd.) (JIS Z1522 to the provisions) paste, tensile strength required when peeling the tape at a rate of 90 ° direction in 50 mm / min with respect to bonding surface a (gf / cm) was measured 5 times, and the average value It was calculated as the peel strength (gf / cm). The results are shown in Table 1. As the value of this peel strength is high, are evaluated as adhesion strength between the current collector and the electrode layer is high.

Figure JPOXMLDOC01-appb-T000004

The evaluation electrode (1) to (17) are those having an electrode layer formed by the electrode-forming slurry containing the modified polymer of the present invention, both a high leveling property can be obtained, it is apparent adhesion strength of the electrode layer is high.
On the other hand, the evaluation electrode (18) to (20) are those having an electrode layer formed by the electrode forming slurry modifying polymer is not contained, either, leveling property is low and it is evident that the adhesion strength of the electrode layer is small.

Claims (11)

  1. (A) and modifying polymer having a sulfonic acid (salt) groups, (B) electrode forming composition which comprises a binder resin.
  2. Wherein (B) the relative 100 parts by mass of the binder resin (A) electrode forming composition according to claim 1, the amount of the modifying polymer is characterized in that 1 to 50 parts by weight.
  3. Wherein (A) according to claim 1 or an electrode-forming composition according to claim 2 polymer forming the modifying polymer is characterized in that it is a copolymer having a block structure.
  4. (A) the polymer forming the modifying polymer, according to claim 1 or claim 2, characterized in that obtained by polymerizing a monomer having a sulfonic acid (salt) group electrode-forming composition.
  5. Polymer forming the (A) modifying polymer,
    (A) a monomer having a sulfonic acid (salt) group, and,
    Monomer (b) having an acid (salt) groups, according to at least one monomer selected from the group of monomers having a skeleton derived from a monomer and an ethylene oxide or propylene oxide having a hydroxyl group claim 1 or the electrode-forming composition according to claim 2, characterized in that a copolymer.
  6. (A) the modifying polymer electrode according to claim 5 which contains a component due to a monomer having a carboxylic acid (salt) groups, characterized in that its content is less than 20 mol% forming composition.
  7. Wherein (a) a monomer having a sulfonic acid (salt) groups, claim 5 or claim, wherein the isoprene sulfonic acid (salt) or (meth) acrylamido-2-methylpropane sulfonic acid (salt) electrode-forming composition according to claim 6.
  8. The monomer having a carboxylic acid (salt) groups, electrode forming composition according to any one of claims 5 to claim 7, characterized in that itaconic acid (salt).
  9. Electrode-forming composition according to claims 1 to 8, (C) a dispersing medium and (D) electrode forming slurry, which comprises an electrode active material.
  10. Electrode, characterized in that it comprises an electrode layer formed by the electrode forming slurry of claim 9 on at least one surface of the current collector.
  11. Electrochemical device characterized by comprising comprises an electrode according to claim 10.
PCT/JP2010/064249 2009-08-24 2010-08-24 Composition for forming electrode, slurry for forming electrode, electrode, and electrochemical device WO2011024789A1 (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128182A1 (en) * 2011-03-18 2012-09-27 日本ゼオン株式会社 Slurry composition for negative electrode of lithium ion secondary cell, negative electrode of lithium ion secondary cell, and lithium ion secondary cell
JP2012204303A (en) * 2011-03-28 2012-10-22 Nippon Zeon Co Ltd Rechargeable battery electrode, a secondary battery electrode binder, a manufacturing method and a secondary battery
WO2013018887A1 (en) * 2011-08-03 2013-02-07 日本ゼオン株式会社 Conductive adhesive composition for electrochemical element electrode, collector with adhesive layer, and electrochemical element electrode
JP2013041819A (en) * 2011-07-15 2013-02-28 Nippon Zeon Co Ltd Composite particle for electrochemical element negative electrode, electrochemical element negative electrode material, and electrochemical element negative electrode
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JP2014026868A (en) * 2012-07-27 2014-02-06 Denso Corp Cathode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery
CN103918111A (en) * 2011-11-07 2014-07-09 电气化学工业株式会社 Binder composition for electrode
WO2014118963A1 (en) * 2013-02-01 2014-08-07 株式会社 日立製作所 Negative electrode material for lithium ion secondary batteries
JP2015022956A (en) * 2013-07-22 2015-02-02 Jsr株式会社 Slurry for power storage device, power storage device electrode, separator and power storage device
WO2015015598A1 (en) * 2013-07-31 2015-02-05 株式会社日立製作所 Coating material for negative electrode active materials for lithium ion secondary batteries, negative electrode active material for lithium ion secondary batteries coated with said coating material, and lithium ion secondary battery using said negative electrode active material in negative electrode
WO2015052809A1 (en) * 2013-10-10 2015-04-16 株式会社日立製作所 Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries using same, lithium ion secondary battery and battery system
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08203499A (en) * 1995-01-25 1996-08-09 Namitsukusu Kk Conductive composition and electrode using this composition
JPH09320604A (en) * 1996-05-28 1997-12-12 Japan Synthetic Rubber Co Ltd Conductive-binded composition for secondary battery electrode and manufacture thereof
JP2002134171A (en) * 2000-10-23 2002-05-10 Mitsubishi Chemicals Corp Lithium secondary battery
JP2002319401A (en) * 2001-04-19 2002-10-31 Hitachi Maxell Ltd Hydrogen storage alloy electrode paste, hydrogen storage alloy electrode and hydride secondary battery
WO2007088979A1 (en) * 2006-02-02 2007-08-09 Jsr Corporation Polymer composition, paste for use in electrode for secondary battery, and electrode for secondary battery
JP2009059514A (en) * 2007-08-30 2009-03-19 Sony Corp Negative electrode and battery
JP2009123523A (en) * 2007-11-15 2009-06-04 Jsr Corp Binder composition for battery electrode, method of manufacturing the same, paste for battery electrode, battery electrode, and method of manufacturing battery electrode

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08203499A (en) * 1995-01-25 1996-08-09 Namitsukusu Kk Conductive composition and electrode using this composition
JPH09320604A (en) * 1996-05-28 1997-12-12 Japan Synthetic Rubber Co Ltd Conductive-binded composition for secondary battery electrode and manufacture thereof
JP2002134171A (en) * 2000-10-23 2002-05-10 Mitsubishi Chemicals Corp Lithium secondary battery
JP2002319401A (en) * 2001-04-19 2002-10-31 Hitachi Maxell Ltd Hydrogen storage alloy electrode paste, hydrogen storage alloy electrode and hydride secondary battery
WO2007088979A1 (en) * 2006-02-02 2007-08-09 Jsr Corporation Polymer composition, paste for use in electrode for secondary battery, and electrode for secondary battery
JP2009059514A (en) * 2007-08-30 2009-03-19 Sony Corp Negative electrode and battery
JP2009123523A (en) * 2007-11-15 2009-06-04 Jsr Corp Binder composition for battery electrode, method of manufacturing the same, paste for battery electrode, battery electrode, and method of manufacturing battery electrode

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128182A1 (en) * 2011-03-18 2012-09-27 日本ゼオン株式会社 Slurry composition for negative electrode of lithium ion secondary cell, negative electrode of lithium ion secondary cell, and lithium ion secondary cell
JP5861845B2 (en) * 2011-03-18 2016-02-16 日本ゼオン株式会社 Lithium-ion secondary battery negative electrode slurry composition, a lithium ion secondary battery negative electrode, and a lithium ion secondary battery
JP2012204303A (en) * 2011-03-28 2012-10-22 Nippon Zeon Co Ltd Rechargeable battery electrode, a secondary battery electrode binder, a manufacturing method and a secondary battery
JP2013041819A (en) * 2011-07-15 2013-02-28 Nippon Zeon Co Ltd Composite particle for electrochemical element negative electrode, electrochemical element negative electrode material, and electrochemical element negative electrode
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 (en) * 2011-08-03 2013-02-07 日本ゼオン株式会社 Conductive adhesive composition for electrochemical element electrode, collector with adhesive layer, and electrochemical element electrode
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
CN103918111A (en) * 2011-11-07 2014-07-09 电气化学工业株式会社 Binder composition for electrode
EP2779286A4 (en) * 2011-11-07 2015-08-05 Denki Kagaku Kogyo Kk Binder composition for electrode
US9257239B2 (en) 2011-11-07 2016-02-09 Denka Company Limited Binder composition for electrode
JP2013168272A (en) * 2012-02-15 2013-08-29 Jsr Corp Binder composition for electrode, slurry for electrode, electrode, and power storage device
JP2014026868A (en) * 2012-07-27 2014-02-06 Denso Corp Cathode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery
WO2014118963A1 (en) * 2013-02-01 2014-08-07 株式会社 日立製作所 Negative electrode material for lithium ion secondary batteries
JP6023222B2 (en) * 2013-02-01 2016-11-09 株式会社日立製作所 Negative electrode material for a lithium ion secondary battery
JP2015022956A (en) * 2013-07-22 2015-02-02 Jsr株式会社 Slurry for power storage device, power storage device electrode, separator and power storage device
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