CN102742051A - Binder particles for electrochemical element - Google Patents

Binder particles for electrochemical element Download PDF

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Publication number
CN102742051A
CN102742051A CN2010800630769A CN201080063076A CN102742051A CN 102742051 A CN102742051 A CN 102742051A CN 2010800630769 A CN2010800630769 A CN 2010800630769A CN 201080063076 A CN201080063076 A CN 201080063076A CN 102742051 A CN102742051 A CN 102742051A
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China
Prior art keywords
polymer
quaternary ammonium
electrode
binder particles
acid
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CN2010800630769A
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Chinese (zh)
Inventor
胁坂康寻
小林佳
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Zeon Corp
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Nippon Zeon Co Ltd
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Publication of CN102742051A publication Critical patent/CN102742051A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • 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

Abstract

Disclosed is a binder for an electrochemical element, which does not contain any component that is decomposed at a voltage at which lithium is inserted into a negative electrode active material, and has excellent output properties ad life properties without being increased in internal resistance. Specifically disclosed are binder particles for an electrochemical element, each of which is composed of a core part and a shell part, and is characterized in that the shell part comprises a polymer that contains a monomer unit containing an atom having a lone pair wherein the atom is converted into the form of a quaternary cation with an organic acid.

Description

The electro chemical elements use binder particles
Technical field
The present invention relates to a kind of binder particles, its emulsion and electro-chemical element electrode and use paste compound; Described binder particles, its emulsion and electro-chemical element electrode are used paste compound; Be used in the manufacturing of the electrode that electrochemical elements such as lithium rechargeable battery or double electric layer capacitor use (below, be generically and collectively referred to as " electrode for electrochemical device " sometimes).
Background technology
Utilized effectively that small-sized, light weight and energy density are high, the needs of the electrochemical elements such as lithium rechargeable battery, double electric layer capacitor and lithium-ion capacitor of rechargeable characteristic enlarge just rapidly.The energy density of lithium rechargeable battery is bigger, therefore, is used to fields such as mobile phone or subnotebook PC.In addition, but therefore the double electric layer capacitor fast charging and discharging, is used as the memory reserve Miniature Power Unit of PC etc.And then double electric layer capacitor also enjoys expectation as the application of the large-scale power supply of used for electric vehicle.In addition, effectively utilized the mixed capacitor of lithium rechargeable battery and double electric layer capacitor advantage,, therefore, received much concern because energy density and output density are all high.
The electrode of these electrochemical elements is made up of collector body and the electrode active material layer that on collector body, supports.Electrode active material layer is to be coated on the collector body and to carry out drying through the electrod composition slurry that will contain decentralized media such as electrode active material, adhesive resin and water and also contain electric conducting material, dispersant, surfactant, viscosity modifier etc. as required to form.These compositions all impact the characteristic of electrochemical element, and particularly the volume of adhesive in electrod composition is higher, therefore, influence the performance of electrochemical element greatly.
Mostly common employed adhesive is the elastomeric polymer particulate.(patent documentation 1) that such elastomeric polymer particulate normally obtains through the emulsion polymerisation of using low-molecular-weight surfactant.Therefore, in the elastomeric polymer that obtains, contain surfactant.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 10-302797 communique
Summary of the invention
The problem that invention will solve
But, for low molecular weight surfactants, in electrochemical element, be exposed under the situation of repeated charge, under the situation that particularly current potential when discharging and recharging is high, decompose sometimes.Therefore; The elastomeric polymer that use contains surfactant is during as the electro chemical elements use binder particles; Sometimes can produce the foreign matter that the analyte because of surfactant causes under the current potential when lithium is inserted into negative electrode active material, cause the internal resistance rising of electrochemical element, battery life to reduce.On the other hand, when utilizing washing to wait the amount that makes surfactant to reduce in the use amount that reduces surfactant or after emulsion polymerisation, the dispersion stabilization of elastomeric polymer reduces sometimes, causes thickization of particle thereby cohesion takes place.
In addition, when using the higher electrode active material of pH as electrode active material, collector body possibly be corroded and produce gas, and the result produces pin hole etc. at electrode surface.
Therefore; The object of the present invention is to provide a kind of electro chemical elements use adhesive; This electro chemical elements use adhesive does not contain the current potential that is inserted in negative electrode active material at lithium and issues the composition of separating estranged; Can not make internal resistance increase and output characteristic, life characteristic excellent, even and under the situation of using the high electrode active material of pH, also can be suppressed at electrode surface and produce pin hole.
The method of dealing with problems
The present invention who solves above-mentioned problem contains following content as main points.
(1) a kind of electro chemical elements use binder particles; This binder particles comprises nuclear portion and shell portion; And shell portion comprises following polymer, and said polymer contains and comprises the monomeric unit with the right atom of isolated electron, and wherein said atom has carried out cationation of quaternary ammonium with organic acid.
(2) according to (1) described electro chemical elements use binder particles, wherein, the weight average molecular weight of said polymer is 5,000 ~ 100,000.
(3) according to (1) or (2) described electro chemical elements use binder particles; Wherein, The polymer that constitutes shell portion has in the right bond thing of isolated electron this and has the right atom of isolated electron and carry out cationation of quaternary ammonium and obtain containing with organic acid; Have 1 mole in a right atom of isolated electron with respect to said, the organic acid use amount that is used for said cationation of quaternary ammonium is 0.5 ~ 2.0 mole.
(4) according to each described electro chemical elements use binder particles in (1) ~ (3); Wherein, The polymer that forms nuclear portion is an elastomeric polymer, and said elastomeric polymer is any polymer in fluorine-based polymer, diolefinic polymer and the acrylic polymer.
(5) a kind of electro chemical elements use adhesive composition, wherein, said composition disperses in decentralized medium that each described electro chemical elements use binder particles forms in above-mentioned (1) ~ (4).
(6) according to above-mentioned (5) described electro chemical elements use adhesive composition, wherein, said decentralized medium is a water.
(7) a kind of electro-chemical element electrode is used paste compound, and it contains each described electro chemical elements use binder particles, electrode active material and decentralized medium in above-mentioned (1) ~ (4).
(8) a kind of electro-chemical element electrode, it is coated on collector body on paste compound above-mentioned (7) described electro-chemical element electrode and carries out drying and make.
(9) a kind of electrochemical element, it has above-mentioned (8) described electrode.
(10) manufacturing approach of a kind of above-mentioned (1) described electro chemical elements use binder particles, this manufacturing approach comprises following operation:
Carry out polymerization to containing the polymerizable composition, polymerizable composition that comprises monomer, obtain comprising operation with the right bond thing (I) of isolated electron with the right atom of isolated electron;
Have that the right atom of isolated electron carries out cationation of quaternary ammonium and the operation that obtains polymer (II) with organic acid to contained in this polymer (I); And
In the presence of polymer (II), make the operation of elastomeric polymer.
The invention effect
Electro chemical elements use binder particles of the present invention does not contain and is exposed to the composition that high potential following time can decompose, for example surfactant etc. repeatedly.Therefore, the electrochemical element of the electro chemical elements use binder particles of the application of the invention can be realized the element long lifetime.In addition; Although electro chemical elements use binder particles of the present invention does not contain surfactant and shows superior dispersion stability yet; Even and use and to contain Ni compound etc. and make material that the pH when making electrode slurry uprises as electrode active material, also can obtain the pole plate of surface smoothing.
Embodiment
(electro chemical elements use binder particles)
Electro chemical elements use binder particles of the present invention has the so-called nucleocapsid structure that is made up of nuclear portion and shell portion.
The polymer that forms nuclear portion is an elastomeric polymer, and above-mentioned elastomeric polymer is preferably any polymer in fluorine-based polymer, diolefinic polymer, the acrylic polymer.Elastomeric polymer is defined as the material that at normal temperatures modulus of elasticity (Young's modulus) is about 1 ~ 10MPa (JIS K 6251).Through making the polymer that forms nuclear portion is above-mentioned polymer, can obtain the excellent pole plate of flexibility and dhering strength.In elastomeric polymer, from can improving proof voltage, and the viewpoint that can improve the energy density of electrochemical element considers, more preferably diolefinic polymer or acrylic polymer, special preferred acrylate base polymer.
Diolefinic polymer is meant, contains the polymer of the monomeric unit that is formed by butadiene, isoprene equiconjugate diene polymerization.The ratio of the monomeric unit that is formed by polymerization of conjugated dienes in the diolefinic polymer is generally more than the 40 weight %, is preferably more than the 50 weight %, more preferably more than the 60 weight %.As diolefinic polymer, can enumerate: the homopolymers of polybutadiene, polyisoprene equiconjugate diene; But the copolymer of the monomer of conjugated diene and copolymerization.But, can enumerate: α such as acrylonitrile, methacrylonitrile, alpha, beta-unsaturated nitriles compound as the monomer of above-mentioned copolymerization; Styrene monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl naphthalene, 1-chloro-4-methyl-benzene, methylol styrene, AMS, divinylbenzene; Unsaturated carboxylic acid such as acrylic acid, methacrylic acid class; Olefines such as ethene, propylene; The monomer of halogen atom-containing such as vinyl chloride, vinylidene chloride; Vinyl esters such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinylpyridine, vinyl imidazole etc. contain the heterocycle vinyl compound.Wherein, preferred α, alpha, beta-unsaturated nitriles compound or styrene monomer, unsaturated carboxylic acid class.But be derived from preferred 5 ~ 60 weight % of ratio of construction unit of the monomer of these copolymerization, further preferred 10 ~ 50 weight %.
Acrylic polymer is meant, contains the polymer of the monomeric unit that is polymerized by acrylic acid ester and/or methacrylate.The ratio of the monomeric unit that is polymerized by acrylic acid ester and/or methacrylate in the acrylic polymer is generally more than the 40 weight %, is preferably more than the 50 weight %, more preferably more than the 60 weight %.As acrylic polymer, can enumerate: the homopolymers of acrylic acid ester and/or methacrylate, acrylic acid ester and/or methacrylate and can with the copolymer of the monomer of its copolymerization.But as the monomer of above-mentioned copolymerization, can enumerate: ethylene glycol dimethacrylate, diglycol dimethylacrylate, trimethylolpropane triacrylate etc. have the carboxylic acid ester monomer of two above carbon-to-carbon double bonds; Styrene monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl naphthalene, 1-chloro-4-methyl-benzene, methylol styrene, AMS, divinylbenzene; Unsaturated carboxylic acid such as acrylic acid, methacrylic acid class; Acrylamide, N hydroxymethyl acrylamide, acrylamide-amide-type monomers such as 2-methyl propane sulfonic acid; α such as acrylonitrile, methacrylonitrile, the alpha, beta-unsaturated nitriles compound; Olefines such as ethene, propylene; Dienes such as butadiene, isoprene monomer; The monomer of halogen atom-containing such as vinyl chloride, vinylidene chloride; Vinyl esters such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinylpyridine, vinyl imidazole etc. contain the heterocycle vinyl compound.Wherein, preferred α, alpha, beta-unsaturated nitriles compound or styrene monomer, preferred especially α, alpha, beta-unsaturated nitriles compound.But the ratio of construction unit that is derived from the monomer of these copolymerization is preferably 3 ~ 60 weight %, further is preferably 5 ~ 50 weight %, is preferably 5 ~ 30 weight % especially.
In the present invention, the glass transition temperature of elastomeric polymer is preferably below 25 ℃, more preferably-100 ℃ ~+25 ℃, further be preferably-80 ℃ ~+10 ℃, most preferably be-80 ℃ ~ 0 ℃.Glass transition temperature through making elastomeric polymer is in above-mentioned scope; The characteristics such as adaptation of flexibility, caking property and coiling property, electrode active material layer and current collector layer are balance highly, thus preferred, in addition; Can keep bonded dose of state that is covered of electrode active material particle surface; Therefore, can suppress that adhesive peels off from electrode active material in the pole plate stamping procedure, reduce thereby can suppress dhering strength.
It is two or more that these elastomeric polymers can use or make up use separately.
Shell portion comprises following polymer, and this polymer contains and comprises monomeric unit with the right atom of isolated electron and this atom and carried out cationation of quaternary ammonium (below, be sometimes referred to as " quaternary ammonium polymer ") by organic acid.
As having the right atom of isolated electron, for example can enumerate: nitrogen, sulphur, oxygen, fluorine, phosphorus etc., wherein, consider from the aspect of versatility and operation property, more preferably nitrogen, sulphur, wherein, nitrogen.
Therefore,, for example can enumerate: by having amino α, the monomeric unit that β ethene property polymerizable compound is derived as comprising monomeric unit with the right atom of isolated electron.Contain amino α; β ethene property polymerizable compound; Particularly; Comprise acrylic acid dimethylamino methyl esters, esters of acrylic acids such as the amino propyl ester of acrylic acid diethylamino methyl esters, acrylic acid dibutylamino methyl esters, acrylic acid dihexyl amino methyl, acrylic acid dimethylamino ethyl ester, acrylic acid diethylamino ethyl ester, acrylic acid two (tert-butyl group) amino ethyl ester, acrylic acid two isohesyl amino ethyl esters, acrylic acid dihexyl, the amino own ester of acrylic acid two (tert-butyl group) and corresponding methyl acrylic ester etc.
In addition, can enumerate 2-vinylpyridine etc. and contain fragrant same clan monomer of nitrogen etc.
These comprise the monomer with the right atom of isolated electron and can use separately also and can make up use.
In addition, but quaternary ammonium polymer can contain the unit by other monomer derived that comprises monomer with the right atom of isolated electron and copolymerization.
But other monomer of above-mentioned copolymerization is preferably the α with organic acid group; β ethene property polymerizable compound comprises for example esters of acrylic acid and corresponding methyl acrylic esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, acrylamide-2-methyl propane sulfonic acid.These can use separately also can make up use.
In addition; Other monomer beyond above-mentioned is preferably does not have organic acid group and amino α; β ethene property polymerizable compound, for example can enumerate: the alkyl or cycloalkyl ester of acrylic acid or methacrylic acid, ethylene glycol dimethacrylate, diglycol dimethylacrylate, trimethylolpropane triacrylate etc. have the carboxylic acid ester monomer of two above carbon-to-carbon double bonds; Styrene monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl naphthalene, 1-chloro-4-methyl-benzene, methylol styrene, AMS, divinylbenzene; Acrylamide, N hydroxymethyl acrylamide, acrylamide-amide-type monomers such as 2-methyl propane sulfonic acid; α such as acrylonitrile, methacrylonitrile, the alpha, beta-unsaturated nitriles compound; Olefines such as ethene, propylene; Dienes such as butadiene, isoprene monomer; The monomer of halogen atom-containing such as vinyl chloride, vinylidene chloride; Vinyl esters such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinylpyridine, vinyl imidazole etc. contain the heterocycle vinyl compound.These can use separately also can make up use.
In quaternary ammonium polymer; Not special qualification of ratio that comprises monomeric unit with the right atom of isolated electron and other monomeric unit; But the content that comprises the monomeric unit with the right atom of isolated electron is preferably with respect to total formation unit of polymer scope at 20 ~ 90 weight %; Further preferably in the scope of 30 ~ 80 weight %, particularly preferably in the scope of 40 ~ 70 weight %, most preferably in the scope of 40 ~ 50 weight %.Comprise monomeric unit through in polymer, containing with the right atom of isolated electron with above-mentioned scope; Can be to have cationic functional group on the surface effectively in the shell portion of adhesive; Can reduce the moving resistance of the lithium ion of inside battery through this cationic functional group, improve the acceptability and the output characteristic of lithium ion.
As stated, quaternary ammonium polymer contains and comprises monomeric unit with the right atom of isolated electron and this atom by the organic acid cationation of quaternary ammonium.Through in quaternized, using organic acid, then and the functional group on collector body surface between form good tunicle easily, thereby can suppress the corrosion of collector body.In addition, even under the situation of using the high electrode active material of pH, also can be suppressed at electrode surface and produce pin hole.
As above-mentioned organic acid, can enumerate the acid that is selected from carboxylic acid, sulfonic acid and the phosphonic acids.
As carboxylic acid, can enumerate: aliphat saturated carboxylic acid such as acetate, butyric acid, trimethylace tonitric, 2 ethyl hexanoic acid, caproic acid, sad, capric acid, laurate, palmitic acid, stearic acid; Aliphat unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, eicosapentaenoic acid, DHA; Aromatic carboxylic acid such as benzoic acid, cinnamic acid; And carboxylic acid derivates such as monochloro acetate, salicylic acid; Polybasic carboxylic acids such as butanedioic acid, glutaric acid, adipic acid, M-phthalic acid, terephthalic acid (TPA) etc.
As sulfonic acid, can enumerate: 2,4-dichloro benzosulfonic acid, 2,5-dichloro benzosulfonic acid, 3,5-dichloro benzosulfonic acid, 2; 4-dibromobenzene sulfonic acid, 2,5-dibromobenzene sulfonic acid, 3,5-dibromobenzene sulfonic acid, 2,4-diiodo-benzene sulfonic acid, 2,5-diiodo-benzene sulfonic acid, 3; 5-diiodo-benzene sulfonic acid, 2,4-two chloro-5-toluene sulfonic acides, 2,5-two chloro-4-toluene sulfonic acides, 2,4-two bromo-5-toluene sulfonic acides, 2,5-two bromo-4-toluene sulfonic acides, 2; 4-two iodo-5-toluene sulfonic acides, 2,5-two iodo-4-toluene sulfonic acides, 2,4-two chloro-5-methoxy benzenesulfonic acids, 2,5-two chloro-4-methoxy benzenesulfonic acids, 2,4-two bromo-5-methoxy benzenesulfonic acids, 2; 5-two bromo-4-methoxy benzenesulfonic acids, 2,4-two iodo-5-methoxy benzenesulfonic acids, 2,5-two iodo-4-methoxy benzenesulfonic acids, 3,3 '-DCBP-2,2 '-disulfonic acid, 3; 3 '-'-dibromobiphenyl-2,2 '-disulfonic acid, 3,3 '-DIBP-2,2 '-disulfonic acid, 4,4 '-DCBP-2; 2 '-disulfonic acid, 4,4 '-'-dibromobiphenyl-2,2 '-disulfonic acid, 4,4 '-DIBP-2,2 '-disulfonic acid, 4; 4 '-DCBP-3,3 '-disulfonic acid, 4,4 '-'-dibromobiphenyl-3,3 '-disulfonic acid, 4; 4 '-DIBP-3,3 '-disulfonic acid, 5,5 '-DCBP-2,2 '-disulfonic acid, 5; 5 '-'-dibromobiphenyl-2,2 '-disulfonic acid, 5,5 '-DIBP-2,2 '-disulfonic acid etc.
As phosphonic acids; Can enumerate: 1-hydroxy ethylidene-1; 1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl propylidene-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl fourth fork-1,1-di 2 ethylhexyl phosphonic acid, ATMP, 2-phosphonic acids butane-1; 2,4-tricarboxylic acids, methyl di 2 ethylhexyl phosphonic acid, inferior nitrogen trimethylene phosphonic, ethylenediamine tetramethylene phosphonic acid, EDMP, ATMP, hexamethylene diamine tetramethylene phosphonic acid, diethylentriamine pentamethylene phosphonic acids, cyclohexanediamine tetramethylene phosphonic acid.
Wherein, consider that preferred phosphonic acids more preferably contains the phosphonic acids of nitrogen-atoms, preferred especially time nitrogen trimethylene phosphonic from the more significant aspect of the antiseptic effect of collector body.
In quaternary ammonium polymer, having the right atom of isolated electron can be all by quaternized, also can part by quaternized.Quaternised ratio is not special to be limited, but preferably make it with respect to have 1 mole in the right atom of isolated electron be 0.5 ~ 2.0 mole, further be preferably 0.7 ~ 1.8 mole, especially be preferably 0.8 ~ 1.5 mole organic acid as quaternizing agent react realize quaternized.
Quaternized when insufficient, can't fully obtain the reduction effect of above-mentioned lithium ion moving resistance.Quaternized when excessive, produce following problem: in the system residual acid after the slurry stated can reduce when making system pH, diminish the Coulomb repulsion effect of electrode active material particle, therefore, the dispersiveness of slurry reduces.
The weight average molecular weight of quaternary ammonium polymer that constitutes shell portion is preferably 5,000 ~ 100,000 scope, and further preferably 7,500 ~ 50,000 scope, particularly preferably in 10,000 ~ 25,000 scope.Molecular weight through making the ammonium fluidized polymer season reacts when the polymerization of nuclear portion and carries out easily in above-mentioned scope.
The glass transition temperature Tg that constitutes the quaternary ammonium polymer of shell portion is preferably below 50 ℃, further is preferably-15 ~ 25 ℃.The glass transition temperature of quaternary ammonium polymer (Tg) can make also with a spot of use amount that caking property is excellent, pole strength strong, be rich in flexibility when this scope, the suppression process when forming through electrode can easily improve electrode density.
Electro chemical elements use binder particles of the present invention is formed by nuclear portion and shell portion, and said nuclear portion comprises aforesaid elastomeric polymer, and said shell portion comprises quaternary ammonium polymer.The ratio of nuclear portion and shell portion is not special to be limited, and is selected in 10/90 ~ 90/10 scope in weight ratio nuclear portion/shell quality award from the ministry, further preferably in 20/80 ~ 80/20 scope, and the scope particularly preferably in 30/70 ~ 70/30.Ratio through making nuclear portion and shell portion can not damage the reduction effect of the moving resistance of lithium ion in above-mentioned scope, also can keep the stability of binder particles.
Preferred 50nm ~ the 500nm of the number average bead diameter of electro chemical elements use binder particles, further preferred 70nm ~ 400nm.The number average bead diameter of binder particles is when this scope, and the intensity and the flexibility of the electrode that obtains are good.
The form that exists of aforesaid electro chemical elements use binder particles of the present invention does not limit especially; But can preferably obtain through emulsion polymerisation like the said electro chemical elements use binder particles of the present invention in back; Therefore, general is that binder particles is dispersed in the emulsion form that forms in the decentralized medium.
(decentralized medium)
As the decentralized medium of electro chemical elements use binder particles, so long as can make the just not special restriction of the homodisperse material of this binder particles.
As decentralized medium, can make in water and the organic solvent any one.As organic solvent, can enumerate: pentamethylene, annular aliphatic hydro carbons such as cyclohexane; Toluene, xylenes, ethylo benzenes etc. are aromatic hydrocarbon based; Ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, cyclohexanone, hexahydrotoluene, ethyl cyclohexane; Chloride aliphatic hydrocarbons such as carrene, chloroform, carbon tetrachloride; Ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; Nitrile such as acetonitrile, propionitrile; Ethers such as oxolane, ethylene glycol bisthioglycolate ethylether: alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monomethyl methyl ether; N-methyl pyrrolidone, N, amide-types such as dinethylformamide.
These decentralized media can use separately also can mix and two or morely use as mixed solvent.Wherein, the decentralized medium that boiling point is low and volatility is high can be removed at short notice and at low temperatures, so preferred.Particularly, preferred acetone, toluene, cyclohexanone, pentamethylene, oxolane, cyclohexane, xylenes, water or N-methyl pyrrolidone or these mixed solvent, special preferred water.
(manufacturing approach of electro chemical elements use binder particles)
The manufacturing approach of binder particles of the present invention is not special to be limited, but can be by the emulsion polymerisation of above-mentioned polymer as emulsifying agent obtained simply.
The autofrettage that is binder particles of the present invention is characterised in that, contains following operation:
Carry out polymerization to containing the polymerizable composition, polymerizable composition that comprises monomer, obtain comprising operation with the right bond thing (I) of isolated electron with the right atom of isolated electron;
Have that the right atom of isolated electron carries out cationation of quaternary ammonium and the operation that obtains polymer (II) with organic acid to contained in this polymer (I); And
In the presence of polymer (II), make the operation of elastomeric polymer.
It is same as described above that the raw material of polymer (I) promptly comprises monomer and the concrete example of other comonomer and their copolymerization ratio etc. with the right atom of isolated electron.Polymerization is not special to be limited, and can obtain polymer (I) simply through polymerisation in solution.
As the solvent that can be used for above-mentioned polymerisation in solution, comprise the fragrant same clans such as toluene, xylenes; Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Alcohols such as n-butanol, isobutanol, isopropyl alcohol; Ester such as ethyl acetate, n-butyl acetate class etc.These can use separately also can make up use.Preferably to the alcohols of polymer (I) favorable solubility.
In addition, be used for not limiting, comprise peroxide polymerization initiators such as azo class polymerization initiator, benzoyl peroxide such as azodiisobutyronitrile etc. the polymerization initiator of the polymerisation in solution of polymer (I) is special.These polymerization initiators can use separately also can make up use.
Polymerization temperature is not special to be limited, and is generally 40 ~ 180 ℃, is preferably about 60 ~ 150 ℃, and in addition, polymerization time is 2 ~ 8 hours, is preferably about 3 ~ 6 hours.
Utilize such polymerisation in solution to obtain simply comprising and have the right bond thing (I) of isolated electron.
Then, through the right atom of isolated electron that has contained in the polymer (I) is carried out cationation of quaternary ammonium, can obtain above-mentioned polymer (II).At this, employed quaternizing agent and use amount thereof etc. are as stated.
Temperature when quaternized is not special to be limited, and is generally 25 ~ 80 ℃, is preferably about 40 ~ 60 ℃, and in addition, the time of quaternized processing is 1 ~ 5 hour, is preferably about 2 ~ 4 hours.
The polymer that obtains thus (II) is above-mentioned quaternary ammonium polymer, and its various characteristics as stated.
Then, through in the presence of the polymer that obtains (II), making above-mentioned elastomeric polymer, then can obtain electro chemical elements use binder particles of the present invention.
Elastomeric polymer as stated, its manufacturing approach is not special to be limited, but sees from the binder particles aspect that can obtain nucleocapsid structure simply, preferably the emulsion polymerisation of the emulsification through utilizing polymer (II) generates elastomeric polymer.
Concrete the creating conditions of elastomeric polymer can be based on forming as subject polymer and setting aptly.
Polymerization initiator as being used for emulsion polymerisation has no qualification, can use known redox polymerization initator, for example comprises hydrogen peroxide.In addition, preferably under 60 ℃ ~ 90 ℃ temperature, carry out emulsion polymerisation.Polymerization time can recently suitably be selected according to above-mentioned nuclear/shell, but is generally 2 ~ 10 hours, is preferably about 4 ~ 6 hours.In addition,, can use above-mentioned decentralized medium, especially preferably make water as the medium of emulsion polymerisation.
(electro-chemical element electrode is used paste compound)
Electro-chemical element electrode of the present invention is characterised in that with paste compound, contains above-mentioned binder particles and electrode active material.In addition, this paste compound contains decentralized medium, electric conducting material and tackifier etc. such as water as required.
(electrode active material)
Electrode active material is for carrying out the acceptance of electronics and the material of emitting in electrode for electrochemical device.Electrode active material mainly contains lithium rechargeable battery and uses active material with active material, double electric layer capacitor with active material and lithium-ion capacitor.
Lithium ion secondary battery positive electrode can use the active material of can occlusion emitting lithium ion with electrode active material (positive active material), roughly divides for active material that is made up of inorganic compound and the active material that is made up of organic compound.
As the positive active material that constitutes by inorganic compound, can enumerate: the lithium-contained composite metal oxide of transition metal oxide, transient metal sulfide, lithium and transition metal etc.As above-mentioned transition metal, can use Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc.
As transition metal oxide, can enumerate: MnO, MnO 2, V 2O 5, V 6O 13, TiO 2, Cu 2V 2O 3, noncrystalline V 2O-P 2O 5, MoO 3, V 2O 5, V 6O 13Deng, wherein, consider preferred MnO, V from cyclical stability and capacity aspect 2O 5, V 6O 13, TiO 2
As transient metal sulfide, can enumerate: TiS 2, TiS 3, noncrystalline MoS 2, FeS etc.
As lithium-contained composite metal oxide, can enumerate: have layer structure lithium-contained composite metal oxide, have spinel structure lithium-contained composite metal oxide, have the lithium-contained composite metal oxide of olivine-type structure etc.
As lithium-contained composite metal oxide, can enumerate: contain lithium and cobalt oxides (LiCoO with layer structure 2), contain lithium nickel oxide (LiNiO 2), lithium composite xoide of Co-Ni-Mn, the lithium composite xoide of Ni-Mn-Al, the lithium composite xoide of Ni-Co-Al etc.
As lithium-contained composite metal oxide, can enumerate: LiMn2O4 (LiMn with spinel structure 2O 4) or Li ［ Mn that a part of Mn is formed with other transition metal displacement 3/2M 1/2O 4(at this, M is Cr, Fe, Co, Ni, Cu etc.) etc.
As lithium-contained composite metal oxide, can enumerate: Li with olivine-type structure xMPO 4Olivine-type lithium phosphate compound shown in (in the formula, M is selected from least a among Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and the Mo, 0≤x≤2).
As organic compound, for example also can use electroconductive polymers such as polyacetylene, contraposition polyphenyl.
The iron type oxide that lacks conductivity through when reduction is fired, having carbon source material, can be used as the electrode active material that is coated by material with carbon element and uses.In addition, these compounds can be partly to carry out element substitution and the material that forms.Positive electrode active material for lithium ion secondary battery can be the mixture of above-mentioned inorganic compound and organic compound.
Lithium ion secondary battery negative pole can use the active material of can occlusion emitting lithium ion with electrode active material (negative electrode active material), roughly mainly is divided into carbon class active material and non-carbon class active material.
As carbon class active material, can enumerate: carbonaceous material and graphite material.The carbonaceous material ordinary representation; Below 2000 ℃ the carbon precursor is being heat-treated low (low-crystalline) material with carbon element of graphitization that (carbonization) forms; And the graphite material is represented, heat-treats the graphite material of the approaching high crystalline of having of obtaining and graphite through commute graphite property carbon under the temperature more than 2000 ℃.
As carbonaceous material, can enumerate: can easily change the easy graphite property carbon of carbon structure and be the difficult graphite property carbon with the approaching structure of amorphous structure that has of representative with the vitreous carbon through heat treatment temperature.As easy graphite property carbon, can enumerate with the tar asphalt that obtains by oil or coal material with carbon element as raw material, for example can enumerate: coke, carbonaceous mesophase spherules (MCMB), mesophase pitch based carbon fiber, thermal decomposition gas-phase growth of carbon fibre etc.MCMB is meant that the mesophasespherule that generates in the process that the pitch class is heated 400 ℃ of front and back carries out separation and Extraction and the carbon particulate that obtains; The mesophase pitch based carbon fiber is meant, with above-mentioned mesophasespherule growth, merge and the mesophase pitch that obtains as the carbon fiber of raw material.
As difficult graphite property carbon, can enumerate: phenolic resins fired body, polyacrylonitrile based carbon fiber, quasi-isotropic carbon, furfuryl alcohol resin fired body (PFA) etc.
As the graphite material, can enumerate: native graphite, Delanium.As Delanium, heat-treat more than 2800 ℃ the Delanium that forms, more than 2000 ℃ MCMB heat-treated the graphitization MCMB that forms, in that more than 2000 ℃ middle asphalt phase based carbon fiber to be heat-treated the graphitization mesophase pitch based carbon fiber that forms etc. main as negative electrode active material.
As non-carbon class active material, can use elemental metals and alloy and their oxide or the sulfide etc. of lithium metal, formation lithium alloy.
As the elemental metals and the alloy that form lithium alloy, can enumerate: the compound that contains metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn.Wherein, can use the elemental metals of silicon (Si), tin (Sn) or plumbous (Pb) perhaps to comprise the alloy of these atoms or the compound of these metals.
As oxide or sulfide, can enumerate: oxide, carbide, nitride, silicide, sulfide, phosphide etc.Wherein, can use oxides such as tin oxide, manganese oxide, titanium oxide, niobium oxide, vanadium oxide, contain the metallic element that is selected from Si, Sn, Pb and the Ti atom contain the lithium-metal composite oxides material.
As containing lithium-metal composite oxides, can also enumerate Li xTi yM zO 4Shown lithium-titanium composite oxide (0.7 ≦ x ≦ 1.5,1.5 ≦ y ≦ 2.3,0 ≦ z ≦ 1.6, M are Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb) wherein, can use Li 4/3Ti 5/3O 4, Li 1Ti 2O 4, Li 4/5Ti 11/5O 4
Lithium ion secondary battery electrode is generally 1 ~ 50 μ m with the volume average particle size of active material, is preferably 2 ~ 30 μ m.Through making particle diameter in above-mentioned scope, the amount of binder during the preparation paste compound stated after can reducing can suppress the reduction of battery capacity, and can easily paste compound be prepared into the viscosity that is suitable for being coated with, and can access uniform electrode.
And then, use active material as lithium ion secondary battery electrode, also can use the material of giving material through the mechanically modifying method in surface attachment conductivity.
As being used for the electrode active material of double electric layer capacitor, can use the allotrope of carbon usually with electrode.As the concrete example of the allotrope of carbon, can enumerate: active carbon, coalescence benzene, carbon whisker and graphite etc., can use the powder or the fiber of these materials.Preferred electrode active material is an active carbon, particularly, can enumerate: with the active carbon as raw material such as phenolic resins, staple fibre, acrylonitrile resin, pitch and cocoanut shell.
Be used for double electric layer capacitor and be generally 0.1 ~ 100 μ m, be preferably 1 ~ 50 μ m, further be preferably 5 ~ 20 μ m with the volume average particle size of the electrode active material of electrode.
Being used for double electric layer capacitor uses the specific area of the electrode active material of electrode to be 30m 2More than/the g, be preferably 500 ~ 5,000m 2/ g, more preferably 1,000 ~ 3,000m 2/ g.The specific area of electrode active material is big more, and the density of the electrode active material layer that obtains then has the trend that becomes more little, therefore, through suitable selection electrode active material, can obtain having the electrode active material layer of expectation density.
(electrode for electrochemical device is used paste compound)
Electrode for electrochemical device of the present invention contains above-mentioned electrode active material, electro chemical elements use binder particles of the present invention and decentralized medium with paste compound.
In the scope of not damaging the object of the invention, the electro chemical elements use binder particles can perhaps be formed the mixture of different two or more binder particles for structure.In addition, also can contain common binder particles with nucleocapsid structure.That is the electro chemical elements use binder particles of the present invention that, contains more than 0.5 weight portion with respect to binder particles total amount 100 weight portions gets final product.
The amount of binder particles with respect to electrode active material 100 weight portions usually in the scope of 0.1 ~ 50 weight portion, preferably in the scope of 0.5 ~ 20 weight portion, more preferably in the scope of 1 ~ 10 weight portion, particularly preferably in the scope of 1 ~ 5 weight portion.The amount of binder particles is when this scope, and the electrode active material layer that can fully guarantee to obtain and the adaptation of collector body can improve the electrochemical element capacity and reduce internal resistance.
Binder particles for example can be dispersed in for binder particles like latex and so on the state in the water particle or to dispersion liquid carry out pulverous particle that drying obtains; But consider that from the viewpoint that alleviates carrying capacity of environment the preferred adhesive particle is dispersed in the water-based emulsion form that forms in the water.
Electro-chemical element electrode of the present invention is used paste compound, as essential composition, and contains decentralized medium, electric conducting material and tackifier etc. as required with mentioned component.
(decentralized medium)
As the decentralized medium that is used to obtain slurry, same with above-mentioned electro chemical elements use adhesive agent emulsion, can make water usually, as long as but can keep the dispersity of above-mentioned each composition, then also can be with an organic solvent.As organic solvent, for example can enumerate: alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol; Alkyl ketone such as acetone, methyl ethyl ketone; Ethers such as oxolane 、 diox, diethylene glycol dimethyl ether; Amide-types such as DEF, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, methylimidazole alkane ketone; Sulphur such as dimethyl sulfoxide (DMSO), sulfolane kind solvent etc., preferred alcohols.
The amount of the decentralized medium in the slurry for the solid component concentration that can make this slurry usually in the scope of 1 ~ 50 weight %, preferably in the scope of 5 ~ 50 weight %, more preferably in the amount of the scope of 10 ~ 30 weight %.
(electric conducting material)
Also can contain electric conducting material at electro-chemical element electrode of the present invention in paste compound.As electric conducting material, can use conductive carbon such as acetylene black, Ketjen black, carbon black, graphite, gas-phase growth of carbon fibre and CNT.Through using electric conducting material, can improve electrode active material electrically contacting each other, be used for can improving the discharge rate characteristic under the situation of lithium rechargeable battery.The use level of electric conducting material is generally 0 ~ 20 weight portion with respect to electrode active material 100 weight portions, is preferably 1 ~ 10 weight portion.
(tackifier)
Can also contain tackifier at electro-chemical element electrode of the present invention in paste compound.As tackifier, can enumerate: cellulosic polymer and these ammonium salt and alkali metal salts such as carboxymethyl cellulose, methylcellulose, hydroxy propyl cellulose; (modification) gathers (methyl) acrylic acid and these ammonium salt and alkali metal salt; Copolymer, maleic anhydride or the maleic acid of (modification) polyvinyl alcohol, acrylic acid or acrylates and vinyl alcohol or the polyvinyl alcohols such as copolymer of fumaric acid and vinyl alcohol; Polyethylene glycol, PEO, PVP, modified polyacrylic acid, oxidized starch, starch phosphate, casein, various modified starches etc.; Wherein, The ammonium salt of carboxymethyl cellulose and the alkali metal salt foams when the modulation aqueous solution etc. are few, so preferred.In addition, in adhesive of the present invention, do not have contained low molecular weight surfactants in the adhesive in the past, therefore, foaminess is low, through making up these, can obtain level and smooth electrode.
The ammonium salt of carboxymethyl cellulose and the degree of etherification falling of alkali metal salt preferred 0.4 ~ 1.6, further preferred 0.8 ~ 1.5.Degree of etherification falling can be guaranteed the dissolubility of cellulose family in water when this scope.In addition, in adhesive of the present invention, do not have low-molecular-weight surfactant contained in the adhesive in the past, therefore, foaminess is low, through making up these, can obtain level and smooth electrode.At this, degree of etherification falling is meant the substitution value of the replacement body of hydroxyl (3) in carboxymethyl etc. of per 1 the anhydroglucose unit in the cellulose.Can adopt 0 ~ 3 value in theory.It is big more that degree of etherification falling becomes, and the ratio that represent then that the ratio of the hydroxyl in the cellulose reduces more, replaces body increases more, and that degree of etherification falling becomes is more little, representes then that the hydroxyl in the cellulose increases more, replace body to reduce more.Degree of etherification falling (substitution value) can be tried to achieve through following method and formula.
At first, precision weighing sample 0.5 ~ 0.7g carries out ashing in magnetic system crucible.After the cooling, the calcination that obtains is moved in the 500ml beaker, interpolation about 250ml of water and N/10 sulfuric acid 35ml also boiled 30 minutes.With its cooling, add phenolphthalein indicator, utilize N/10 potassium hydroxide that back titration is carried out in excessive acid, calculate substitution value by following formula.
A=(a * f-b * f 1)/sample (g)-basicity (or+acidity)
Substitution value=M * A/ (10000-80A)
A: the N/10 sulfuric acid amount (ml) that the bonding alkali metal ion among the sample 1g is consumed
The use amount of a:N/10 sulfuric acid (ml)
The titer coefficient of f:N/10 sulfuric acid
The titer of b:N/10 potassium hydroxide (ml)
f 1: the titer coefficient of N/10 potassium hydroxide
M: the weight average molecular weight of sample
1 weight % solution viscosity of tackifier (below, abbreviate as " solution viscosity ".) be meant according to JISZ8803:1991 and utilize single cylindrical shape rotation viscometer (25 ℃, rotating speed=60rpm, main shaft shape: No.4) begin to measure value after 1 minute.
Solution viscosity is preferred 1, and is further preferred 2,000 ~ 15 more than the 000mPas, 000mPas.Solution viscosity is when this scope, and electrode active material is coated by tackifier equably, and the polymer that can suppress the shell part in the binder particles of the present invention is adsorbed on the electrode active material surface.
In addition, this carboxymethyl cellulose aqueous solution is as long as use 2,000 ~ 15, and the solution of 000mPa then also can make up use and be lower than 2, the solution of 000mPa.
The use level of tackifier is with respect to electrode active material 100 weight portions, preferred 0.5 ~ 2.0 weight portion.The use level of tackifier when this scope, coating, good with the adaptation of collector body.Need to prove that above-mentioned " (modification) gathers " is meant " unmodified gathering " or " modification gathers ", " (methyl) acrylic acid " is meant " acrylic acid " or " methacrylic acid ".In addition, tackifier can use separately a kind of also can and with two or more.
(other additive)
Except that mentioned component; Electro-chemical element electrode of the present invention be with also can further containing reinforcing material, dispersant, having other compositions such as electrolysis additive that suppress functions such as electrolyte decomposition in the paste compound, also can after contain these compositions in the electrode for electrochemical device stated.These however influence the just not special restriction of cell reaction.
As reinforcing material, can use various inorganic and organically spherical, tabular, bar-shaped or bat wools.Through using reinforcing material, can obtain tough and tensile and soft electrode, can show excellent long-term cycle characteristics.The use amount of reinforcing agent is generally 0.01 ~ 20 weight portion with respect to electrode active material 100 weight portions, is preferably 1 ~ 10 weight portion.Through being included in the above-mentioned scope, can show high power capacity and high load characteristics.
As dispersant, but illustration: anionic property compound, cationic compound, nonionic compound and macromolecular compound.Dispersant can be selected according to the electrode active material and the electric conducting material that use.Electro-chemical element electrode is proportional with containing of the dispersant in the paste compound, is 0.01 ~ 10 weight portion with respect to electrode active material 100 weight portions preferably.Through making containing of dispersant proportional in above-mentioned scope, then the slurry excellent in stability can obtain level and smooth electrode, and can demonstrate high battery capacity.
In addition, can add various additives in paste compound at electro-chemical element electrode.Particularly, can enumerate nanoparticles such as aerosil and gaseous oxidation aluminium.Through mixing nanoparticle, then can control the thixotropy of electro-chemical element electrode with paste compound, further can improve the levelability of the electrode that obtains thus.Electro-chemical element electrode use nanoparticle in the paste compound to contain proportional be 0.01 ~ 10 weight portion with respect to electrode active material 100 weight portions preferably.Through making nanoparticle in above-mentioned scope, then slurry is stable, generative nature is excellent, and demonstrates high battery behavior.
(electro-chemical element electrode is with the manufacturing approach of paste compound)
Electro-chemical element electrode of the present invention is used paste compound, can obtain through mixing above-mentioned electro chemical elements use binder particles, electrode active material, decentralized medium and employed as required tackifier, electric conducting material etc.
Mixed method is not special to be limited, and for example can enumerate the method for the mixing arrangement that uses stirring-type, oscillatory type and rotary type etc.In addition, can enumerate: use homogenizer, ball mill, sand mill, roller mill and planetary mixing roll etc. to disperse the method for kneading device.
The viscosity of slurry is also according to the kind of coating machine and coating line strip and difference is generally 100 ~ 100, and 000mPas is preferably 1,000 ~ 50,000mPas, more preferably 5,000 ~ 20,000mPas.
(manufacturing approach of electrode)
Electrode for electrochemical device of the present invention is that above-mentioned electro-chemical element electrode is coated on the collector body with paste compound and dry and form electrode active material layer and obtain.Collector body is so long as the just not special restriction of material that has conductivity and have the electrochemistry durability, but considers metal materials such as for example preferred iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum from having stable on heating viewpoint.Wherein, use collector body as lithium ion secondary battery positive electrode, preferred especially aluminium is used collector body as negative pole, special preferably copper.The not special restriction of the shape of collector body, preferred thickness is the sheet about 0.001 ~ 0.5mm.In order to improve the adhesive strength of collector body and electrode active material, the collector body that the asperities processing was carried out in preferred use in advance.As the asperities method, can enumerate: mechanical milling method, electrolytic polishing method and chemical grinding method etc.In mechanical milling method, can use set have abrasive particle cloth paper, grinding stone, emery wheel, possess wire brush of steel wire etc. etc.In addition, for adhesive strength and the conductivity that improves electrode active material layer, also can form the intermediate layer on the collector body surface.
The manufacturing approach of electrode, so long as on the single face at least of above-mentioned collector body, the method for the electrode active material layer that layeredly bonds on the preferred two sides gets final product.Electro-chemical element electrode is with the coating process not especially restriction of paste compound to collector body.For example can enumerate: methods such as scraper plate method, infusion process, reverse roll method, direct rolling method, intagliotype, extrusion molding, spread coating.
As the drying means of slurry of coating, for example can enumerate: utilize the drying, vacuumize of warm wind, hot blast, low wet wind, through shining the seasoning that (far) infrared ray or electron beam etc. carry out.The seasoning of wherein, preferably carrying out through the irradiation far infrared.
Preferably can remove baking temperature and drying time the temperature and time of the solvent in the slurry of coating fully, as baking temperature, be 100 ~ 300 ℃, is preferably 120 ~ 250 ℃.As drying time, be generally 10 minutes ~ 100 hours, be preferably 20 minutes ~ 20 hours.
Preferably has following operation: at the above-mentioned electrode slurry of coating on the collector body and after carrying out drying, use moulding press or roll squeezer etc., reduce the porosity of electrode active material layer through pressurized treatments.The temperature of hot pressing is preferably 50 ℃ ~ 150 ℃ scope, more preferably 80 ℃ ~ 130 ℃ scope.The preferred range of porosity is 5% ~ 15%, and preferred scope is 7% ~ 13%.When porosity is too high, charge efficiency and discharging efficiency variation.Porosity is low excessively, produces following problem: be difficult to obtain high volume capacity or electrode active material layer and peel off from collector body easily and produce unfavorable condition.
The thickness of the electrode active material layer that obtains is generally 5 ~ 300 μ m, is preferably 30 ~ 250 μ m.Thickness through making electrode active material layer is in above-mentioned scope, and it is good that the flexibility of electrode and adaptation become.
(electrochemical element)
Electrode of the present invention can be preferably used as the electrode of electrochemical elements such as lithium rechargeable battery, double electric layer capacitor and lithium-ion capacitor especially.Have no qualification as electrochemical element,, further the example that uses electrode of the present invention is elaborated as the electrode of lithium rechargeable battery.
(lithium rechargeable battery)
Have positive pole, negative pole, dividing plate and electrolyte as the lithium rechargeable battery of an example of electrochemical element of the present invention and form, in positive pole and the negative pole is electrode of the present invention one of at least.
(electrolyte)
Electrolyte is not special to be limited, the electrolyte that for example can use in the solvent of non-water class dissolving to form as the lithium salts of supporting electrolyte.As lithium salts, for example can enumerate: LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3SO 3Li, C 4F 9SO 3Li, CF 3COOLi, (CF 3CO) 2NLi, (CF 3SO 2) 2NLi, (C 2F 5SO 2) lithium salts such as NLi.Can preferably use the LiPF that particularly is soluble in solvent and shows high degree of dissociation 6, LiClO 4, CF 3SO 3Li.These can use or mix two or more uses separately.The amount of supporting electrolyte is generally more than the 1 weight % with respect to electrolyte, is preferably more than the 5 weight %, in addition, is generally below the 30 weight %, is preferably below the 20 weight %.When the supporting electrolyte amount is very few or too much, all can cause the charge characteristic of ionic conductance reduction and battery and flash-over characteristic to reduce.
As the solvent that is used for electrolyte; The solvent of supporting electrolyte dissolving is just not special to be limited so long as make, and can use dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC) and methyl ethyl carbonate alkyl carbonate classes such as (MEC) usually; Ester such as gamma-butyrolacton, methyl formate class, 1, ethers such as 2-dimethoxy-ethane and oxolane; Sulfur-containing compound such as sulfolane and dimethyl sulfoxide (DMSO) class.Particularly dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate obtain high ionic conductivity and the serviceability temperature scope is wide easily, so preferred.These can use or mix two or more uses separately.
As the electrolyte beyond above-mentioned, can enumerate: gelatinous polymer electrolyte that forms for polymer dielectrics such as PEO, polyacrylonitrile dipping electrolyte or lithium sulfide, LiI, inorganic solid electrolytes such as Li3N.
In addition, also can in above-mentioned electrolyte, contain additive and use.As electrolysis additive, preferred vinylene carbonate carbonats compounds such as (VC).
(dividing plate)
Dividing plate is the porous substrate with pore portion, has as spendable dividing plate: the porousness dividing plate that (a) has pore portion; (b) on single face or two sides, be formed with the porousness dividing plate of polymeric coating layer; Or (c) form the porousness dividing plate of the porous resin coating contain inorganic ceramic powder; As these nonrestrictive examples, PP type, polyethylene kind, TPO or aromatic polyamide class porousness dividing plate are arranged, be coated with solid macromolecule electrolytes such as Kynoar, PEO, polyacrylonitrile or Kynoar-hexafluoropropylene copolymer with or the dividing plate of the macromolecule membrane used of gel polyelectrolyte, gelation polymeric coating layer or be coated with the dividing plate etc. of the porous rete that constitutes with dispersant by inorganic filler, inorganic filler.
(manufacturing approach of battery)
The manufacturing approach of lithium rechargeable battery is not special to be limited.For example across the superimposed negative pole of dividing plate with anodal and it is reeled or folding etc. according to cell shapes, put into battery case then, and in battery case, inject electrolyte and seal.Can also put into expansion alloy as required or overcurrent such as fuse, PTC element prevent element, stereotype etc., prevent that the pressure of inside battery from rising, cross and discharge and recharge.The shape of battery can be any one in lamination-type, Coin shape, coin shape, sheet type, cylinder type, square, platypelloid type etc.
(embodiment)
Below, the present invention will be described to enumerate embodiment, but the present invention is not limited to this.Need to prove, short of special instruction, part and % in the present embodiment are weight basis.
In embodiment and comparative example, each rerum natura is estimated as follows.
(weight average molecular weight of quaternary ammonium polymer (II))
Utilization is implemented to measure as the gel permeation chromatography that launches solvent with water, calculates the weight average molecular weight of quaternary ammonium polymer (II) with standard polyoxyethylene scaled value.
(electrochemical properties)
(1) cyclic voltammetric titration (CV) is measured
Quaternary ammonium polymer (II) is cast on the glass-carbon electrode of diameter 3mm φ, at 60 ℃ of electrodes that obtained polymer (II) casting down through 5 hours.The casting electrode that use obtains uses the lithium metal to the utmost point and reference electrode, is that 1:2 mixed carbonic acid ethyl and diethyl carbonate obtain mixed solvent with the volume ratio under 25 ℃, in the gained mixed solvent, dissolves LiPF 6Making its concentration is 1 mol, thus obtain electrolyte and in gained electrolyte each electrode of dipping, sweep speed is set at 1mV/sec and measures carrying out cyclic voltammetric titration (below be called CV) under the scope of 0 ~ 3V.The glass-carbon electrode of cast polymerization thing (II) is not also carried out same mensuration.Then; Ratio (following formula) conduct of the current value under the 0.01V during the 0.01V current value down during the CV that will use the electrode of polymer (II) casting to carry out measures is measured with the CV that uses the glass-carbon electrode of cast polymerization thing (II) not to carry out causes the index of the difficulty of decomposition, judges with following benchmark.Following ratio is more little representes that then anti-decomposability is more excellent.
[mathematical expression 1]
Figure BDA00001970630400191
SA: be lower than 80%
A:80% is above and be lower than 101%
B:101% is above and be lower than 200%
C:200% is above and be lower than 300%
D:300% is above and be lower than 400%
(charge-discharge characteristic)
(1) initial stage charge-discharge characteristic
Use the stacked type battery that obtains in embodiment and the comparative example; The mode of the constant-current constant-voltage mise-a-la-masse method through said 0.1C is carried out following charge and discharge cycles under 25 ℃ respectively: with constant current charge to 4.2V; Under constant voltage, charge then, and under the constant current of 0.1C, be discharged to 3.0V.The discharge capacity that to represent with percentage, is judged with following benchmark as initial charge with respect to the ratio of charging capacity.The bigger then expression of its value is the few more battery of capacity deterioration at initial stage.
More than the SA:98%
A:96% is above and be lower than 98%
B:92% is above and be lower than 96%
C:88% is above and be lower than 92%
D: be lower than 88%
(2) charge
Use the range upon range of lattice type battery that obtains in embodiment and the comparative example; The mode of the constant-current constant-voltage mise-a-la-masse method through said 0.1C is carried out following charge and discharge cycles under 25 ℃ respectively: constant current charge is to 4.2V; Under constant voltage, charge then, and under the constant current of 0.1C, be discharged to 3.0V.Charge and discharge cycles proceed to 50 times the circulation till, with the 100th time the circulation discharge capacity be the presented higher holdup with respect to likening to of initial stage discharge capacity, judge with following benchmark.Its value is bigger then to be represented to reduce few more by repeating to discharge and recharge the capacity that causes.
More than the SA:85%
A:80% is above and be lower than 85%
B:75% is above and be lower than 80%
C:70% is above and be lower than 75%
D:65% is above and be lower than 70%
E:60% is above and be lower than 65%
F: be lower than 60%
(3) charge-discharge velocity characteristic (part throttle characteristics)
Condition determination is changed to constant current 2.0C, in addition, likewise measure the discharge capacity under each constant current with the mensuration of charge.With percentage calculate under this condition discharge capacity with respect to the ratio of above-mentioned battery capacity and with it as the charge-discharge velocity characteristic, judge with following benchmark.The big more expression internal resistance of its value is more little and can carry out high speed and discharge and recharge.
More than the SA:80%
A:70% is above and be lower than 80%
B:60% is above and be lower than 70%
C:50% is above and be lower than 60%
D:40% is above and be lower than 50%
E: be lower than 40%
(pinhole number of electrode surface)
Make the pole plate of 10cm * 10cm, the spot number (pinhole number) on electrode active material layer surface is estimated with following benchmark.The corrosion that this spot number (pinhole number) is represented collector body more less more less, electrode surface is even more.
A: free of pinholes
B: 1 ~ 5 of pin hole
C: 6 ~ 10 of pin holes
D: 10 ~ 30 of pin holes
E: pin hole is more than 31
(embodiment 1)
In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; 3.0 parts of azodiisobutyronitriles, 60 parts of dimethylaminoethyl methacrylate, 70 parts of butyl acrylates, methyl methacrylate are mixed for 20 parts; And the gained mixed liquor dripped through 3 hours constant speed ground, further make its reaction 3 hours and make polymer (I-1).Again the polymer of making (I-1) is cooled to 60 ℃, adds inferior nitrogen trimethylene phosphonic 145 parts of (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) and 500 parts of making of ion exchange water quaternary ammonium polymers (II-1) as quaternizing agent.The weight average molecular weight of quaternary ammonium polymer (II-1) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-1) is 40% with respect to total formation unit of polymer.
In the quaternary ammonium polymer that obtains (II-1), add 1 part in ferric sulfate and 1 part in ascorbic acid and be warming up to 80 ℃; Again the mixture of 30 parts of 80 parts of butyl acrylates, 40 parts of methyl methacrylates and acrylonitrile and 1 part of aqueous hydrogen peroxide solution and ion exchange water are dripped through 3 hours constant speed ground respectively for 50 parts simultaneously; Make its reaction 5 hours again; Obtain with quaternary ammonium polymer (II-1) as shell portion, with the binder particles dispersion of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer) as the nucleocapsid structure of nuclear portion.Dispersion to obtaining concentrates, and obtains solid component concentration and be 40% binder particles emulsion.In addition, the ratio of the construction unit that is derived from acrylonitrile in the nuclear portion is 20%.
(manufacturing of negative pole)
Using 1% solution viscosity is 2, the carboxymethyl cellulose of 000mPas (Daicel chemical industry Co., Ltd. system " Daicel2200 ") modulation 1% aqueous solution.
In the planetary mixer of band disperser, put into 100 parts of Delaniums, add 100 parts of the above-mentioned aqueous solution therein, be adjusted to solid component concentration 53.5% with ion exchange water after, mixed 60 minutes down at 25 ℃.Then, be adjusted to solid component concentration 44% with ion exchange water after, mixed 15 minutes down in 25 ℃ again.
Then, put into and be scaled 2 parts the above-mentioned binder particles emulsion that obtains with solid constituent, further mixed 10 minutes.Under reduced pressure it is carried out deaeration and handle, obtain the electrode slurry of good fluidity.
Use some coating machine (Comma coater); And be that mode about 200 μ m is coated on above-mentioned slurry composition for electrode on the Copper Foil of thickness 20 μ m with dried thickness; Speed with 0.5m/min is following dry 2 minutes at 60 ℃; Under 120 ℃, carry out 2 minutes heat treated, obtain electrode blank (former anti-).Utilize roll squeezer that this electrode blank is rolled, the negative pole that obtains electrode active material layer thickness and be 80 μ m is used electrode.
(anodal manufacturing)
Utilize planetary mixer at LiNiO as positive active material 2Mixing as the aqueous dispersions of the above-mentioned binder particles emulsion of adhesive 2.5 parts (solid component concentration 40%), as the degree of etherification falling of tackifier in 100 parts is that 0.8 40 parts (solid component concentrations 2%) of carboxymethyl cellulose aqueous solution and an amount of water obtain positive pole and uses slurry.This positive pole is coated on slurry on the aluminium foil of thickness 18 μ m and at 50 ℃ down after dry 20 minutes, under 150 ℃, carries out 2 hours heat treated, then, carrying out roll-in and obtaining electrode active material layer thickness is that the positive pole of 100 μ m is used electrode.
The laminated film manufacture batteries container that the resin-coated that the two sides of use aluminium flake is made up of polypropylene forms.Then, use above-mentioned positive pole and negative pole and remove electrode active material layer from the end respectively, and weld the Ni lug, at the position welding Cu lug (タ Block) of removing electrode active material layer of negative pole in the position of removing electrode active material layer of positive pole.With the positive pole that obtains and negative pole with the opposed mode clamping of the two poles of the earth electrode active material layer face by the dividing plate that the micro-porous film of polyethylene system constitutes, reel and be accommodated in the above-mentioned battery case.Next, to wherein injecting electrolyte, said electrolyte is to be with the concentration dissolving LiPF of 1 mol in the mixed ethylene carbonate of 1:2 and the mixed solvent that diethyl carbonate forms with the volume ratio under 25 ℃ 6Form.Then, sealing laminated film, the lithium rechargeable battery of making lamination-type.The evaluation result of the performance of this battery is shown in table 2.
(embodiment 2)
As negative electrode active material, use lithium titanate (Li 4Ti 5O 12) replace Delanium, in addition, carry out the operation same with embodiment 1, make the lithium rechargeable battery of emulsion, electrode slurry, electrode and Coin shape of the binder particles of nucleocapsid structure, and estimate.The result is shown in table 1, table 2.
(embodiment 3)
The quaternary ammonium polymer that obtains among the embodiment 1 (II-1) is warming up to 50 ℃; The mixture of 30 parts of 80 parts of butadiene, 40 parts of styrene and acrylonitrile and 0.3 part of potassium peroxydisulfate and ion exchange water are dripped through 4 hours constant speed ground respectively for 50 parts simultaneously; Make its reaction 6 hours again, obtain with quaternary ammonium polymer (II-1) as shell portion, with the dispersion of phenylethylene/butadiene/acrylonitrile copolymer (elastomeric polymer) as the nucleocapsid structure binder particles of nuclear portion.Dispersion to obtaining concentrates, and obtains solid component concentration and be the emulsion of 40% binder particles.Except with it as the binder particles emulsion, carry out the operation same with embodiment 1, make the lithium rechargeable battery of electrode slurry, electrode and Coin shape, and estimate.The result is shown in table 1, table 2.
(embodiment 4)
The mixture that in the quaternary ammonium polymer that obtains (II-1), adds 12 parts of 98 parts of butyl acrylates, 40 parts of methyl methacrylates and acrylonitrile replaces the mixture of 30 parts of 80 parts of butyl acrylates, 40 parts of methyl methacrylates and acrylonitrile; In addition; Carry out the operation same with embodiment 1; The lithium rechargeable battery of emulsion, electrode slurry, electrode and the Coin shape of the binder particles of making nucleocapsid structure, and estimate.The result is shown in table 1, table 2.In addition, the ratio of the construction unit that is derived from acrylonitrile in the nuclear portion is 8%.
(embodiment 5)
The mixture that in the quaternary ammonium polymer that obtains (II-1), adds 42 parts of 80 parts of butyl acrylates, 28 parts of methyl methacrylates and acrylonitrile replaces the mixture of 30 parts of 80 parts of butyl acrylates, 40 parts of methyl methacrylates and acrylonitrile; In addition; Carry out the operation same with embodiment 1; The lithium rechargeable battery of emulsion, electrode slurry, electrode and the Coin shape of the binder particles of making nucleocapsid structure, and estimate.The result is shown in table 1, table 2.In addition, the ratio of the construction unit that is derived from acrylonitrile in the nuclear portion is 28%.
(embodiment 6)
In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 3.0 parts of azodiisobutyronitriles, 27 parts of dimethylaminoethyl methacrylate, 96 parts of butyl acrylates and methyl methacrylate and obtain mixed liquor for 27 parts; And through 3 hours these mixed liquors of constant speed ground dropping; Make its reaction 3 hours again, make polymer (I-2).Again the polymer of making (I-2) is cooled to 60 ℃; Interpolation is made quaternary ammonium polymer (II-2) as 500 parts of the inferior nitrogen trimethylene phosphonic of quaternizing agent 70 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) and ion exchange waters.The weight average molecular weight of quaternary ammonium polymer (II-2) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-2) is 18% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-2) to replace quaternary ammonium polymer (II-1); In addition, carry out the operation same, make with quaternary ammonium polymer (II-2) as shell portion, with the emulsion of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer) as the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1; The lithium rechargeable battery of electrode slurry, electrode and Coin shape, and estimate.The result is shown in table 1, table 2.
(embodiment 7)
In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 3.0 parts of azodiisobutyronitriles, 48 parts of dimethylaminoethyl methacrylate, 85 parts of butyl acrylates and methyl methacrylate and obtain mixed liquor for 20 parts; And through 3 hours these mixed liquors of constant speed ground dropping; Make its reaction 3 hours again, make polymer (I-3).Again the polymer of making (I-3) is cooled to 60 ℃; Interpolation is made quaternary ammonium polymer (II-3) as 500 parts of the inferior nitrogen trimethylene phosphonic of quaternizing agent 70 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) and ion exchange waters.The weight average molecular weight of quaternary ammonium polymer (II-3) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-3) is 32% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-3) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-3) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 8)
In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 3.0 parts of azodiisobutyronitriles, 72 parts of dimethylaminoethyl methacrylate, 60 parts of butyl acrylates and methyl methacrylate and obtain mixed liquor for 15 parts; And through 3 hours these mixed liquors of constant speed ground dropping; Make its reaction 3 hours again, make polymer (I-4).Again the polymer of making (I-4) is cooled to 60 ℃; Interpolation is made quaternary ammonium polymer (II-4) as 500 parts of the inferior nitrogen trimethylene phosphonic of quaternizing agent 174 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) and ion exchange waters.The weight average molecular weight of quaternary ammonium polymer (II-4) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-4) is 48% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-4) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-4) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 9)
In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 3.0 parts of azodiisobutyronitriles, 96 parts of dimethylaminoethyl methacrylate and butyl acrylate and obtain mixed liquor for 54 parts; And through 3 hours these mixed liquors of constant speed ground dropping; Make its reaction 3 hours again, make polymer (I-5).Again the polymer of making (I-5) is cooled to 60 ℃; Interpolation is made quaternary ammonium polymer (II-5) as 500 parts of the inferior nitrogen trimethylene phosphonic of quaternizing agent 232 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) and ion exchange waters.The weight average molecular weight of quaternary ammonium polymer (II-5) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-5) is 64% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-5) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-5) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 10)
Quaternizing agent as polymer (I-1); Use acetate 25 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition, carry out the operation same, make quaternary ammonium polymer (II-6) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-6) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-6) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-6) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-6) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 11)
Quaternizing agent as polymer (I-1); Use p-methyl benzenesulfonic acid 72 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is about 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition; Carry out the operation same, make quaternary ammonium polymer (II-7) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-7) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-7) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-7) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-7) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 12)
In the making of polymer (I-1); In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 0.8 part of azodiisobutyronitrile, 60 parts of dimethylaminoethyl methacrylate, 70 parts of butyl acrylates and 20 parts of methyl methacrylates and it is dripped through 3 hours constant speed ground; Make its reaction 5 hours again, make polymer (I-8), as the quaternizing agent of polymer (I-8); Use acetate 25 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition, carry out the operation same, make quaternary ammonium polymer (II-8) with embodiment 1; Making, and is estimated as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer) as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with quaternary ammonium polymer (II-8).In addition, the weight average molecular weight of quaternary ammonium polymer (II-8) is 6,000.The result is shown in table 1, table 2.
The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-8) is 40% with respect to total formation unit of polymer.
(embodiment 13)
In the making of polymer (I-1); In reactor, pack into 40 parts of methyl ethyl ketones and under blanket of nitrogen, be warming up to 120 ℃; Mix 5 parts of azodiisobutyronitriles, 60 parts of dimethylaminoethyl methacrylate, 70 parts of butyl acrylates and methyl methacrylate and obtain mixed liquor for 20 parts; And, make polymer (I-9), as the quaternizing agent of polymer (I-9) through 3 hours these mixed liquors of constant speed ground dropping; Use acetate 25 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition, carry out the operation same, make quaternary ammonium polymer (II-9) with embodiment 1; Making, and is estimated as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer) as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with quaternary ammonium polymer (II-9).The result is shown in table 1, table 2.
In addition, the weight average molecular weight of quaternary ammonium polymer (II-9) is 80,000.The content of monomer (dimethylaminoethyl methacrylate) unit that have the right atom of isolated electron comprising in the quaternary ammonium polymer (II-9) is 40% with respect to total formation unit of polymer.
(embodiment 14)
The amount of inferior nitrogen trimethylene phosphonic is made as 43.5 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 0.3 mole), in addition, carries out the operation same, make quaternary ammonium polymer (II-10) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-10) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-10) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-10) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-10) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 15)
The amount of inferior nitrogen trimethylene phosphonic is made as 116 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 0.8 mole), in addition, carries out the operation same, make quaternary ammonium polymer (II-11) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-11) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-11) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-11) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-11) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(embodiment 16)
The amount of inferior nitrogen trimethylene phosphonic is made as 260 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1.8 moles), in addition, carries out the operation same, make quaternary ammonium polymer (II-12) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-12) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-12) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-12) to replace quaternary ammonium polymer (II-1) in addition; Carry out the operation same with embodiment 1; Making, and is estimated as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer) as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with quaternary ammonium polymer (II-12).The result is shown in table 1, table 2.
(embodiment 17)
The amount of inferior nitrogen trimethylene phosphonic is made as 435 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 3 moles), in addition, carries out the operation same, make quaternary ammonium polymer (II-13) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-13) is 25,000.The content of monomer (dimethylaminoethyl methacrylate) unit that in addition, has the right atom of isolated electron comprising in the quaternary ammonium polymer (II-13) is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-13) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-13) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(comparative example 1)
In possessing the adjustable high-pressure reactor of mixer and temperature, be respectively charged into 0.1 part of 200 parts in water, 0.5 part of NaLS, 1.0 parts of potassium peroxydisulfates, 0.5 part of sodium hydrogensulfite and 30 parts of styrene, 39 parts of butadiene, 30 parts of methyl methacrylates, 1 part of itaconic acid, α-styrene dimer thing, under 45 ℃, make its reaction 6 hours.Then; Proceed polymerization at 60 ℃ of mixtures that added down 0.2 part of 45 parts of styrene, 25 parts of butadiene, 20 parts of methyl methacrylates, 1 part of itaconic acid and α-styrene dimer thing continuously, finish the back and under 70 ℃, make its further reaction 6 hours and obtain product adding continuously through 7 hours.The product that obtains is adjusted into 40% and obtain the emulsion of binder particles through the deodorizing enrichment process with solid component concentration.Use the emulsion of the emulsion of above-mentioned binder particles, in addition, carry out the operation same, make the lithium rechargeable battery of emulsion, electrode slurry, electrode and the Coin shape of binder particles, and estimate with embodiment 1 as binder particles.In addition; Electrochemical stability as far as neopelex; In CV measures, do not use casting electrode, use in electrolyte the electrolyte solution of neopelex being dissolved into the concentration of 0.1 weight % and obtaining, measure with the glass-carbon electrode of not casting.Other condition determination and embodiment 1 likewise measure.The result is shown in table 1, table 2.
(comparative example 2)
Quaternizing agent as polymer (I-1); Use phosphatase 24 0 part (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition, carry out the operation same, make quaternary ammonium polymer (II-14) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-14) is 25,000, and the content that comprises monomer (dimethylaminoethyl methacrylate) unit with the right atom of isolated electron is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-14) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-14) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(comparative example 3)
Quaternizing agent as polymer (I-1); Use methyl iodide 60 parts (molal quantity with respect to the nitrogen-atoms in the dimethylaminoethyl methacrylate is 1 mole) to replace 145 parts of time nitrogen trimethylene phosphonics; In addition; Carry out the operation same, make quaternary ammonium polymer (II-15) with embodiment 1.The weight average molecular weight of quaternary ammonium polymer (II-15) is 25,000, and the content that comprises monomer (dimethylaminoethyl methacrylate) unit with the right atom of isolated electron is 40% with respect to total formation unit of polymer.
As quaternary ammonium polymer; Use quaternary ammonium polymer (II-15) to replace quaternary ammonium polymer (II-1); In addition; Carry out the operation same, make with quaternary ammonium polymer (II-15) as shell portion, with the lithium rechargeable battery of butyl acrylate/methyl methacrylate/acrylonitrile copolymer (elastomeric polymer), and estimate as emulsion, electrode slurry, electrode and the Coin shape of the binder particles of the nucleocapsid structure of nuclear portion with embodiment 1.The result is shown in table 1, table 2.
(comparative example 4)
As negative electrode active material, use lithium titanate (Li 4Ti 5O 12) replace Delanium, in addition, carry out the operation same with comparative example 2, make the lithium rechargeable battery of emulsion, electrode slurry, electrode and the Coin shape of nucleocapsid structure binder particles, and estimate.The result is shown in table 1, table 2.
(comparative example 5)
As negative electrode active material, use lithium titanate (Li 4Ti 5O 12) the replacement Delanium.In addition, carry out the operation same, make the lithium rechargeable battery of emulsion, electrode slurry, electrode and the Coin shape of nucleocapsid structure binder particles, and estimate with comparative example 3.The result is shown in table 1, table 2.
Table 1
Figure BDA00001970630400301
Table 2
Figure BDA00001970630400311
Result by table 2 can know following content.According to the present invention; Shown in embodiment; Through using shell portion to comprise the binder particles that polymer that monomeric unit with the right atom of isolated electron and this atom formed by the organic acid cationation of quaternary ammonium constitutes by containing; Do not issue the composition of separating estranged owing to do not contain the current potential that is inserted in negative pole at lithium, therefore, electrochemical properties is excellent, charge-discharge characteristic is excellent.In addition, owing to use organic acid, therefore, collector body can not be corroded, and electrode surface is even.
On the other hand; Using surfactant to carry out polymerization; Using shell portion is not the situation (comparative example 1) that comprises the polymer adhesive particle that monomeric unit with the right atom of isolated electron and this atom formed by cationation of quaternary ammonium by containing, or the polymer adhesive particle situation (comparative example 2 ~ 5) of using this atom to be formed by the inorganic acid cationation of quaternary ammonium, electrochemical properties or charge-discharge characteristic variation; Or the corrosion of collector body change is many, and it is inhomogeneous that electrode becomes.

Claims (10)

1. electro chemical elements use binder particles; Said binder particles comprises nuclear portion and shell portion; Said shell portion comprises following polymer; Said polymer contains and comprises the monomeric unit with the right atom of isolated electron, and saidly has the right atom of isolated electron and carried out cationation of quaternary ammonium with organic acid.
2. electro chemical elements use binder particles according to claim 1, wherein, the weight average molecular weight of said polymer is 5,000 ~ 100,000.
3. electro chemical elements use binder particles according to claim 1 and 2, wherein,
The polymer that constitutes shell portion has in the right bond thing of isolated electron this and has the right atom of isolated electron and carry out cationation of quaternary ammonium and obtain comprising with organic acid,
Have 1 mole in a right atom of isolated electron with respect to said, the organic acid use amount that is used for said cationation of quaternary ammonium is 0.5 ~ 2.0 mole.
4. according to each described electro chemical elements use binder particles in the claim 1 ~ 3; Wherein, The polymer that forms nuclear portion is an elastomeric polymer, and said elastomeric polymer is any polymer in fluorine-based polymer, diolefinic polymer and the acrylic polymer.
5. electro chemical elements use adhesive composition, it disperses in decentralized medium, and each described electro chemical elements use binder particles forms in the claim 1 ~ 4.
6. electro chemical elements use adhesive composition according to claim 5, wherein, said decentralized medium is a water.
7. an electro-chemical element electrode is used paste compound, and it contains each described electro chemical elements use binder particles, electrode active material and decentralized medium in the claim 1 ~ 4.
8. electro-chemical element electrode, it is coated on collector body on paste compound the described electro-chemical element electrode of claim 7 and carries out drying and make.
9. electrochemical element, it has the described electrode of claim 8.
10. method of making the described electro chemical elements use binder particles of claim 1, this method comprises following operation:
Carry out polymerization to containing the polymerizable composition, polymerizable composition that comprises monomer, obtain comprising operation with the right bond thing (I) of isolated electron with the right atom of isolated electron;
Have that the right atom of isolated electron carries out cationation of quaternary ammonium and the operation that obtains polymer (II) with organic acid to contained in this polymer (I); And
In the presence of polymer (II), make the operation of elastomeric polymer.
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