CN101550322A - Combination for capacitor electrode adhesive - Google Patents

Combination for capacitor electrode adhesive Download PDF

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Publication number
CN101550322A
CN101550322A CNA2009101326318A CN200910132631A CN101550322A CN 101550322 A CN101550322 A CN 101550322A CN A2009101326318 A CNA2009101326318 A CN A2009101326318A CN 200910132631 A CN200910132631 A CN 200910132631A CN 101550322 A CN101550322 A CN 101550322A
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composition
methyl
quality
polymer
electrode
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CN101550322B (en
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茂木武志
北口博纪
铃木浩史
伊藤一聪
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Yinnenshi Materials Co ltd
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JSR Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/13—Energy storage using capacitors

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

Abstract

The invention relates to a combination for capacitor electrode adhesive, capable of providing the serum with excellent electrochemistry stability and adhesive ability of afflux body for forming the electrode and uniformity of coating when the afflux body is porous and the serum unable of blocking the afflux body grid. The combination for capacitor electrode adhesive comprises the polymer combination comprising (a) component: fluorine polymer 5-20 weight% and (b) component: (methyl) acrylics polymer 80-95 weight% containing the structure unit of the monomer represented by the general formula (1), namely granular polymer combination with number-average grain size of 0.1-0.4 Mum, general formula (1) CH2=CR1COOR2, in the general formula (1), R1 represents hydrogen atom or methyl, R2 represents alkyl or cycloalkyl of carbon atom number 1-18.

Description

Combination for capacitor electrode adhesive
Technical field
The present invention relates to be used to obtain the combination for capacitor electrode adhesive of electrode for capacitors suitable on electrical condensers such as double charge layer capacitor, lithium-ion capacitor.
Background technology
In recent years, miniaturization and light-weighted surprising development along with electronics have also proposed miniaturization and light-weighted high request for the battery as power supply.In order to satisfy such requirement, develop various store batteries, for example nickel-hydrogen accumulator, lithium-ions battery etc. are all dropped into actual the use.
On the other hand, as the Electrical storage devices that is used for the high-power characteristic that vehicle mounted, power tool use etc., develop the electrical condenser that the lithium-ion capacitor, double charge layer capacitor etc. of chemical reaction do not take place at electrode.
Because the surface-area of gac is big, so be suitable for the electrode active material that double charge layer capacitor that conduct forms or lithium-ion capacitor are used on the interface of electrode and electrolytic solution.But, because its surface-area is big, for gac is sticked on the collector, have to use a large amount of tackiness agent (caking agent), the problem that resulting electrode for capacitors forms the high electrode for capacitors of internal resistance takes place in its result, therefore in order to address this problem, seek the strong tackiness agent of bonding force.
In addition, as the tackiness agent that is used for electrode for capacitors, because the occasion that this electrode for capacitors uses as positive pole, be exposed to well-oxygenated environment for a long time, the occasion as negative pole uses is exposed to reducing environment for a long time, therefore, must possess enough electrochemical stabilities.
As the tackiness agent that is used to make electrode for capacitors, generally use fluorine resins such as the tetrafluoroethylene of electrochemical stability or polyvinylidene difluoride (PVDF).
But the electrode for capacitors that uses these fluorine resins to make is because the bonding force of this fluorine resin is not enough, so the problem that exists electrode active material to come off from collector.
In order to solve the problem that this electrode active material comes off,, for example propose a kind of use and contain from monomeric unit 10～55 quality % of conjugated diene compound and the composition (referring to Patent Document 1) of simple function aromatic ethylene compound as tackiness agent.
But there is the problem that does not possess enough electrochemical stabilities in this patent documentation 1 disclosed tackiness agent.
In addition, in lithium-ion capacitor, need be in the electrode active material of negative pole the operation of elements doped lithium, and, in order to carry out this operation,, must use the porous metallic substance, rather than existing tinsel as collector.Therefore, seek to be used to make the slurries of the electrode for capacitors of lithium-ion capacitor, can obtain the porous collector is had the proterties of well applied property.
Yet, apply the occasion of slurries as water class material, because the surface energy height of water is not easy homogenizing, according to circumstances, depression etc. can take place, be difficult to apply equably.At such problem, generally take to make slurries form proper viscosity, thereby obtain the method for high uniformity by using carboxymethyl cellulose (CMC) etc.
But, will can block the grid of this collector by adjusting the occasion on the porous collector that slurries that viscosity has high uniformity are coated to especially little aperture, the electrode for capacitors that causes obtaining forms the electrode that hinders lithium doping.
Patent documentation 1 TOHKEMY 2005-64294 communique
Summary of the invention
The present invention has considered above content and has finished, its purpose is to provide a kind of combination for capacitor electrode adhesive that slurries can be provided, the electrochemical stability of these slurries and all good to the adhesivity of the collector that constitutes electrode, when this collector is the porous occasion, also can obtain homogeneity when applying these slurries, and can not block the grid of collector.
Further investigation through the inventor, found that as the material that constitutes combination for capacitor electrode adhesive, the material that contains specific fluorine type polymer and specific (methyl) acrylic polymers by use, modulate as full-bodied slurries, use these slurries to be not easy to block grid, thereby finished content of the present invention.
Combination for capacitor electrode adhesive of the present invention is characterised in that, contain polymer composition (A) and dispersion medium (B), this polymer composition (A) by (a) composition fluorine type polymer 5～20 quality % and (b) monomer structure unitary (methyl) acrylic polymers 80～95 quality % that contain from following general formula (1) expression of composition constitute, it is the granular polymer composition of number average bead diameter 0.1～0.4 μ m.
General formula (1) CH 2=CR 1COOR 2
(in above-mentioned general formula (1), R 1Expression hydrogen atom or methyl, R 2The alkyl or cycloalkyl of expression carbonatoms 1～18.)
In combination for capacitor electrode adhesive of the present invention, preferably contain the structural unit of 80～95 quality % with respect to whole 100 quality % of described fluorine type polymer from vinylidene as the fluorine type polymer of above-mentioned (a) composition.
In addition, in combination for capacitor electrode adhesive of the present invention, preferably contain the structural unit of 10～35 quality % with respect to whole 100 quality % of described (methyl) acrylic polymers from methyl methacrylate as (methyl) acrylic polymers of above-mentioned (b) composition.
In addition, in combination for capacitor electrode adhesive of the present invention, preferably has the structure after above-mentioned (a) composition and compoundization of above-mentioned (b) composition.
And then, in combination for capacitor electrode adhesive of the present invention, preferred above-mentioned polymer composition be by the granule that constitutes with (a) composition as nucleus, use the monomer of above-mentioned general formula (1) expression to carry out the nucleus polymerization and obtain.
Combination for capacitor electrode adhesive of the present invention, as the material that constitutes it, owing to contain specific fluorine type polymer, so can obtain basic electrochemical stability, and then because when containing specific (methyl) acrylic polymers with specific ratio, this combination for capacitor electrode adhesive forms the granular composition with specific number average bead diameter, so at collector is the porous occasion, can obtain homogeneity during coating and be not easy to block grid, thereby, even in the occasion of the electrode for capacitors that will obtain, still can obtain good electrode activity, can not hinder lithium doping as the electrode use of lithium-ion capacitor.
Embodiment
Below will specifically describe the present invention.
[polymer composition (A)]
Combination for capacitor electrode adhesive of the present invention (being designated hereinafter simply as " tackiness agent composition ") is for containing the granular composition of polymer composition (hereinafter referred to as " specific polymer composition "), this polymer composition by (a) composition fluorine type polymer 5～20 quality % and (b) (methyl) acrylic polymers 80～95 quality % of containing from the monomer structure unit (hereinafter referred to as " specific (methyl) acrylic compound ") of above-mentioned general formula (1) expression of composition constitute.
[(a) composition: fluorine type polymer]
Constituting tackiness agent of the present invention uses (a) composition fluorine type polymer in the specific polymer composition of composition as long as be fluorine-containing polymkeric substance, then do not limit especially, but more particularly, preferably can enumerate to make and contain (a-1) vinylidene fluoride and (a-2) polymkeric substance that obtains of the polymerizable monomer polymerization of R 1216.
In addition, as the polymerizable monomer that is used to form (a) composition fluorine type polymer,, also can contain the polymkeric substance of other unsaturated monomers for (a-3) except above-mentioned (a-1) vinylidene fluoride with (a-2) the R 1216.
As (a-3) other unsaturated monomers, can enumerate (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems; Multifunctional (methyl) acrylic compound such as ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate; Aromatic ethylene compounds such as vinylbenzene, alpha-methyl styrene, Vinylstyrene; Vinyl esters such as vinyl-acetic ester, propionate; Vinyl halides compounds such as vinylidene, tetrafluoroethylene, vinylchlorid, vinylidene chloride; (b-2) described later beyond divinyl, isoprene, chloroprene equiconjugate dienes, the ethene contains functional group's unsaturated monomer etc.These unsaturated monomers can independent a kind of use, perhaps is used in combination.
Ratio from the structural unit (hereinafter referred to as " vinylidene fluoride composition ") of (a-1) vinylidene fluoride that contains in (a) composition, preferably the whole 100 quality % with respect to (a) composition contain 80～95 quality %, more preferably 85～95 quality %, preferred especially 88～93 quality %.
Because the vinylidene fluoride components in proportions is in above-mentioned scope, so (a) composition and (b) the consistency height between the composition can obtain being not easy to produce the polymer composition of layer separation phenomenon.
Particularly as the electrode adhesive composition, has such (a) composition of aftermentioned and (b) under the situation of the polymer composition of the structure (hereinafter referred to as " composite structure ") after compoundization of composition, this layer separation phenomenon becomes distinct issues in use.That is, (a) granule of composition formation is difficult to carry out the nucleus polymerization of (b) composition as nucleus.
In addition, ratio from the structural unit (hereinafter referred to as " R 1216 composition ") of (a-2) R 1216 that contains in (a) composition, preferably the whole 100 quality % with respect to (a) composition contain 2～20 quality %, more preferably 2～15 quality %, preferred especially 2～10 quality %.
Because the R 1216 components in proportions is in above-mentioned scope, so (a) composition and (b) the consistency height between the composition can obtain being not easy to produce the polymer composition of layer separation phenomenon.
And then, ratio from the structural unit (hereinafter referred to as " other unsaturated monomer composition ") of other unsaturated monomer of (a-3) that contain in (a) composition, preferably the whole 100 quality % with respect to (a) composition contain 0～30 quality %, more preferably 0～20 quality %, preferred especially 0～10 quality %.
Because other unsaturated monomer components in proportions is in above-mentioned scope, so (a) composition and (b) the consistency height between the composition can obtain being not easy to produce the polymer composition of layer separation phenomenon.
[(b) composition: (methyl) acrylic polymers]
As constituting tackiness agent of the present invention with (b) composition in the specific polymer composition of composition: (methyl) acrylic polymers, preference contains functionalized base polymer as enumerating, and it is specially monomer (b-1) (methyl) alkyl acrylate of above-mentioned general formula (1) expression and contains that polymerizable monomer polymerization that (b-2) contain functional group's unsaturated monomer obtains.
As (b-1) (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems etc.
Contain the functional group of containing in functional group's unsaturated monomer as (b-2), can enumerate carboxyl, carboxylic acid anhydride, amide group, amino, cyano group, epoxy group(ing), vinyl, sulfonic group etc.Wherein, preferred carboxyl, amide group, epoxy group(ing), cyano group, sulfonic group.
Contain functional group's unsaturated monomer as what have a carboxyl, for example can enumerate unsaturated monocarboxylic classes such as vinylformic acid, (methyl) vinylformic acid, Ba Dousuan; Unsaturated polycarboxylic acid classes such as toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid; Contain above-mentioned unsaturated polycarboxylic acid free carboxy alkyl ester or contain amides of free carboxy etc.
Contain functional group's unsaturated monomer as what have a carboxylic acid anhydride, for example can enumerate the anhydrides of above-mentioned unsaturated carboxylic acid etc.
Contain functional group's unsaturated monomer as what have an amide group, for example can enumerate (methyl) acrylamide, α-propenyl chloride acid amides, N, N '-methylene radical (methyl) acrylamide, N, unsaturated carboxylic acid amidess such as N '-ethylidene (methyl) acrylamide, N-methylol (methyl) acrylamide, N-2-hydroxyethyl (methyl) acrylamide, N-2-hydroxypropyl (methyl) acrylamide, N-3-hydroxypropyl (methyl) acrylamide, Ba Dousuan acid amides, toxilic acid diamide, fumaric acid diamide.
As having the amino functional group's unsaturated monomer that contains, for example can enumerate (methyl) acrylic-amino methyl esters, (methyl) vinylformic acid N-methylamino-methyl esters, (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid 2-amino ethyl ester, (methyl) vinylformic acid 2-methylamino-ethyl ester, (methyl) vinylformic acid 2-ethylamino ethyl ester, (methyl) vinylformic acid 2-dimethylaminoethyl, (methyl) vinylformic acid 2-lignocaine ethyl ester, (methyl) vinylformic acid 2-n-propylamine base ethyl ester, (methyl) vinylformic acid 2-n-butyl amine base ethyl ester, the amino propyl ester of (methyl) vinylformic acid 2-, (methyl) vinylformic acid 2-methylamino-propyl ester, (methyl) vinylformic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) vinylformic acid 3-, (methyl) vinylformic acid 3-methylamino-propyl ester, the aminoalkyl ester class of unsaturated carboxylic acids such as (methyl) vinylformic acid 3-dimethylamino propyl ester; N-dimethylamino methyl (methyl) acrylamide, N-2-amino-ethyl (methyl) acrylamide, N-2-methylamino-ethyl (methyl) acrylamide, N-2-ethylamino ethyl (methyl) acrylamide, N-2-dimethylaminoethyl (methyl) acrylamide, N-2-diethyllaminoethyl (methyl) acrylamide, N-3-aminopropyl (methyl) acrylamide, N-3-methylamino-propyl group (methyl) acrylamide, the N-aminoalkyl group derivatives class of unsaturated carboxylic acid acid amides such as N-3-dimethylamino-propyl (methyl) acrylamide etc.
Contain functional group's unsaturated monomer as what have cyano group, for example can enumerate unsaturated carboxylic acid nitriles such as methacrylonitrile, α-Lv Bingxijing, vinylidene cyanogen; The cyano group alkyl esters of unsaturated carboxylic acids such as (methyl) 2 cyanoethyl acrylate, (methyl) vinylformic acid 2-cyano group propyl ester, (methyl) vinylformic acid 3-cyano group propyl ester etc.
Contain functional group's unsaturated monomer as what have an epoxy group(ing), for example can enumerate glycidyl methacrylate, methacrylic glycidyl ether etc. and contain unsaturated group Racemic glycidol compound etc.
As having the sulfonic functional group's of containing unsaturated monomer, for example can enumerate 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid (salt), isoprene sulfonic acid (salt) etc.
More than containing functional group's unsaturated monomer can a kind of independent use, also can be used in combination.
In addition, as the method that contains functionalized base polymer that obtains having imported vinyl, for example can enumerate the polymkeric substance that contains carboxyl and the above-mentioned esterification that contains unsaturated group Racemic glycidol compound, contain epoxy group(ing) polymkeric substance and the above-mentioned esterification that contains functional group's unsaturated monomer with carboxyl, contain the polymkeric substance of carboxyl and above-mentionedly have the amino amidate action that contains functional group's unsaturated monomer, contain amino polymkeric substance and the above-mentioned amidate action that contains functional group's unsaturated monomer etc. with carboxyl.
In addition, as forming the employed polymerizable monomer of (b) composition (methyl) acrylic polymers, contain functional group's unsaturated monomer except above-mentioned (b-1) (methyl) alkyl acrylate with (b-2), also can use (b-3) to contain the composition of other unsaturated monomer.
As (b-3) other unsaturated monomer that can contain, for example can enumerate as above-mentioned (a-3) other unsaturated monomer cited, multifunctional (methyl) acrylic compound, aromatic ethylene compound, vinyl esters, ethylene halide compounds, conjugated diene, ethene etc.
Ratio from the structural unit (hereinafter referred to as " (methyl) alkyl acrylate composition ") of (b) (b-1) (methyl) alkyl acrylate that composition contained preferably contains 50～98 quality % with respect to whole 100 quality % of (b) composition, more preferably 60～95 quality %, preferred especially 70～90 quality %.
Because (methyl) alkyl acrylate components in proportions is in above-mentioned scope, so (a) composition and (b) the consistency height between the composition can obtain being not easy to produce the polymer composition of layer separation phenomenon.In addition, when the occasion of (methyl) alkyl acrylate components in proportions above 98 quality %, the tackiness agent that obtains can excessively volumetric expansion in slurries with composition.
As (b) composition that constitutes in the tackiness agent usefulness specific polymer composition of composition of the present invention, preferably contain structural unit (hereinafter referred to as " methyl methacrylate composition ") especially from the methyl methacrylate of conduct (methyl) alkyl acrylate composition, and, when (b) composition is the occasion that contains the methyl methacrylate composition, this methyl methacrylate components in proportions, when (b) composition whole are 100 quality %, be preferably 10～35 quality %, more preferably 15～33 quality %, preferred especially 20～30 quality %.
Because the methyl methacrylate components in proportions is in above-mentioned scope, so can obtain the tackiness agent composition better with the adhesivity of collector.
And, the ratio that contains the structural unit (hereinafter referred to as " containing functional group's unsaturated monomer composition ") of functional group's unsaturated monomer from (b) (b-2) that composition contained, when (b) composition whole are 100 quality %, be preferably 0.1～20 quality %, more preferably 0.5～18 quality %, preferred especially 1.0～15 quality %.
When (b-2) contains the occasion of 0.1 whole quality % of functional group's unsaturated monomer components in proportions deficiency (b) composition, the reactant particulate chemical stability that obtains in the polymerization process that uses it is low, is difficult to obtain good water dispersion medium.On the other hand, when (b-2) contains the occasion that functional group's unsaturated monomer components in proportions surpasses 20 whole quality % of (b) composition, the reactant particulate excess stickiness height that in the polymerization process that uses it, obtains, above-mentioned reactant particle unification ground aggegation, its result is difficult to obtain good water dispersion medium.
And then, ratio from the structural unit (hereinafter referred to as " other unsaturated monomer composition ") of (b) (b-3) other unsaturated monomer that composition contained, when (b) composition whole are 100 quality %, be preferably 0～40 quality %, more preferably 0～30 quality %, preferred especially 0～20 quality %.
Because other unsaturated monomer components in proportions is in above-mentioned scope, so (a) composition and (b) the consistency height between the composition can obtain being not easy to produce the polymer composition of layer separation phenomenon.
Constituting tackiness agent of the present invention, contain fluorine type polymer 5～20 quality %, preferred 8～15 quality % as (a) composition with in the specific polymer composition of composition.
The occasion of the fluorine type polymer less than 5 quality % that contain in polymer composition, the tackiness agent that obtains can form the low composition of chemical resistant properties with composition.On the other hand, the fluorine type polymer that contains in polymer composition surpasses the occasion of 20 quality %, and the tackiness agent that obtains can form the low composition of bonding force with composition.And then, in the occasion that makes the electrical condenser high rate discharge that finally obtains, there are low problem of electrostatic capacity and the problem that can't obtain good cycle characteristics.
[number average bead diameter]
The number average bead diameter of polymer composition of the present invention is 0.1～0.4 μ m, is preferably 0.2～0.4 μ m.In addition, preferred 1/3 littler than the number average bead diameter of bonding electrode active material of the number average bead diameter of tackiness agent.
When the occasion of the number average bead diameter less than 0.1 μ m of tackiness agent, when polymerization and when making slurries, owing to disperse the unstable defective that causes producing easy generation agglutinator.On the other hand, surpass the occasion of 0.4 μ m, the bonding deficiency of counting when producing the tackiness agent that adds same amount, the defective of the poor adhesion of pole plate when the number average bead diameter of tackiness agent.
[measuring method of number average bead diameter]
The number average bead diameter of polymer composition of the present invention is to use the He-Ne laser (value that λ=632.8nm) measures for the determination of light scattering device " ALV5000 " of light source (manufacturing of ALV company) of 22mW.
Preferred its fusing point (Tm) of polymer composition is below 170 ℃, more preferably 0～110 ℃, and preferred especially 30～60 ℃.When the fusing point (Tm) of tackiness agent surpasses the occasion of 170 ℃ of temperature, this tackiness agent lacks flexibility and cementability, and the tendency of the adhesivity step-down of the collector of existence and electrode active material.
[structure of polymer composition]
Tackiness agent of the present invention preferably has (a) composition and (b) structure after compoundization of composition, specifically, be preferably granule with (a) composition as nucleus, use the monomer of above-mentioned general formula (1) expression to carry out the nucleus polymerization, thereby form the particle (hereinafter referred to as " composite particle precursor ") of the composite structure of the shell that obtains (b) composition.
[synthesizing of composite particle precursor]
The particulate of the structure after compoundization is fit to synthetic method for example can adopt Japanese kokai publication hei 7-258499 communique disclosed method.
In addition, as nucleus, use the monomer of above-mentioned general formula (1) expression to carry out that the nucleus polymerization is following particularly to be carried out the granule of (a) composition.
Promptly, the fluorine class monomer that at first is used to form (a) composition carries out emulsion polymerization, obtain the granule that fluorine type polymer constitutes, secondly, in the presence of above-mentioned granule, the monomer that use is used to form (methyl) acrylic polymers carries out emulsion polymerization, forms the shell that (b) composition constitutes thus, obtains the particle of composite structure.
[dispersion medium (B)]
As the dispersion medium of electrochemical appliance electrode adhesive of the present invention, can make water with composition.
As mentioned above polymer composition (A) is being carried out the occasion that emulsion polymerization obtains, the water dispersion medium in the time of can continuing to use polymerization re-uses after also can concentrating.
In addition, the dispersion medium of combination for capacitor electrode adhesive of the present invention can be replaced as required and use the organic dispersion medium that is suitable for active substance.
The medium of relevant use has no particular limits, and can enumerate aromatic series carbohydrate, non-aromatic carbohydrate, chloride carbohydrate, nitrogenous carbohydrate, sulfur-bearing carbohydrate etc.
As the object lesson of such organic dispersion medium, can enumerate toluene, N-Methyl pyrrolidone (NMP), methyl iso-butyl ketone (MIBK) (MIBK), pimelinketone, methyl-sulphoxide (DMSO), dimethyl formamide (DMF) etc.
Have no particular limits with the method for the replacement of above-mentioned organic medium, for example can enumerate combination for capacitor electrode adhesive of the present invention is added in the solvent, make the method for moisture evaporation by underpressure distillation; The moisture that volatilizees from combination for capacitor electrode adhesive of the present invention is dissolved into method in the solvent arbitrarily again with the solids component that obtains.
The concentration of (A) composition in the binder composition can suitably be set according to the kind difference of (B) composition that uses, so that form maneuverable range of viscosities.
In addition, electrode adhesive of the present invention preferred 15～50 quality % of solid component concentration of composition, more preferably 20～40 quality %.Situation greater than 50% because tackiness agent becomes big with the viscosity of composition, exists the operation in the mixed processes such as weighing to become situation of difficult.On the other hand, the situation less than 15% for active substance, conductive carbon etc., exists with the solids component conversion and adds a certain amount of tackiness agent, and then the solids component of electrode slurries can reduce, and can not produce the situation of the electrode of expectation thickness.
In the present invention, " solids component conversion " be meant the composition of from composition, removing dispersion medium.
Aforesaid tackiness agent composition is suitable as the tackiness agent that is used to obtain the electrode that uses at electrical condensers such as double charge layer capacitor, lithium-ion capacitors and uses.Tackiness agent composition of the present invention is suitable as the combination for capacitor electrode adhesive that has used the porous collector especially and uses.And then, use as the relevant combination for capacitor electrode adhesive of lithium-ion capacitor.
[electrode for capacitors]
By on collector, applying the dry slurries that contain tackiness agent of the present invention with the electrode active material of composition and gac etc., obtain electrode for capacitors.
[electrode active material]
The electrode active material that is used to obtain electrode for capacitors preferably is the powder of 100 meshes of 3～400 μ m by particle diameter.
When the situation of electrode for capacitors,, for example can enumerate MnO as electrode active material as the positive pole use 2, MoO 3, V 2O 5, V 6O 13, Fe 2O 3, Fe 3O 4, Li (1-x)CoO 2, Li (1-x)NiO 2, Li xCo ySn zO 2, Li (1-x)Co (1-y)Ni yO 2, TiS 2, TiS 3, MoS 3, FeS 2, CuF 2, NiF 2In mineral compound; The carbon material of gac, fluorocarbons, graphite, gas-phase growth of carbon fibre and/or its crushed products, PAN carbon fiber and/or its crushed products, asphalt-based carbon fiber and/or its crushed products etc.; Polyacetylene, poly-electroconductive polymer to benzene etc.; Polyacetylene class organic semiconductor etc.Wherein, special, using gac and polyacetylene class organic semi-conductor occasion, it is good to obtain charge, and electrical condenser capacious.
On the other hand, when the situation of electrode for capacitors as the negative pole use, as electrode active material, for example can preferably enumerate the carbon material of fluorocarbons, graphite, gas-phase growth of carbon fibre and/or its crushed products, PAN carbon fiber and/or its crushed products, asphalt-based carbon fiber and/or its crushed products etc.; Polyacetylene, poly-electroconductive polymer to benzene etc.; The noncrystalline compound that the compound of tin-oxide or fluorine etc. constitutes; Polyacetylene class organic semiconductor etc.Especially, in the occasion of the graphite material that uses the high natural graphite of carbonizing degree or synthetic graphite, greying mesocarbon etc., it is good to obtain charge, and electrical condenser capacious.
Use the occasion of carbon material as electrode active material, the median size of this carbon material for example is preferably 0.1～50 μ m, and more preferably 1～45 μ m is in the scope of preferred especially 3～40 μ m.
[collector]
As the collector that is used to obtain electrode for capacitors, for example can enumerate Ni mesh, the punch metal that plates Ni, expander metal, metal spun yarn net, foamed metal, net metal fiber sintering body etc.
[slurries]
Be used to obtain the slurries of electrode for capacitors, tackiness agent can be mixed with the various additives that add as required with composition and electrode active material and modulate.
Tackiness agent is with the consumption of composition, and for 100 mass parts electrode active materials, preferred adhesive converts by solids component with composition and contains 0.1～20 mass parts, more preferably 0.5～10 mass parts, preferred especially 1～10 mass parts.
When the tackiness agent occasion of composition, can not obtain good adhesion with collector for 100 mass parts electrode active material less thaies, 0.1 mass parts.On the other hand, use composition for the occasion of 100 mass parts electrode active materials above 20 mass parts when tackiness agent, the internal resistance of the electrode for capacitors that obtains is excessive, and the tackiness agent that obtains does not possess good electrical characteristic.
As the method that on the surface of collector, applies slurries, can adopt the method for any high precision coating unit of rotary roller method, comma scraper method (コ Application マ バ one), woodburytype, air knife method etc.
In addition, carry out the exsiccant method as the slurries that apply on the surface to collector, for example except the method that leaves standstill seasoning, can adopt the drying means of use fan drying machine, warm braw drying machine, infrared heating machine or FAR INFRARED HEATING machine etc. etc.
Drying temperature generally is preferably set to 20～250 ℃, more preferably is set at 130～170 ℃.In addition, be preferably set to 1～120 minute time of drying, more preferably be set at 5～60 minutes.
As the various additives that in slurries, add as required, can enumerate viscosity adjustment that the water solvent that uses is had a solubility with conductive agents such as conductive carbon, metal-powder such as polymkeric substance, graphite etc.As the viscosity adjustment polymkeric substance that the water solvent that uses is had solubility, for example the water solvent of Shi Yonging is the occasion of water, then can enumerate cellulosic polymer and salt thereof such as carboxymethyl cellulose, Natvosol, hydroxypropylcellulose; Polyvinyl alcohol, poly-(methyl) vinylformic acid and salt thereof; The multipolymer of polyoxyethylene glycol, polyvinylpyrrolidone, vinylformic acid or its salt and vinyl alcohol etc.
Combination for capacitor electrode adhesive as described above, owing to contain specific fluorine type polymer as the material that constitutes it, can obtain basic electrochemical stability, and then because when containing specific (methyl) acrylic polymers with specific ratio, this combination for capacitor electrode adhesive is the granular substance with specific number average bead diameter, can obtain at collector is homogeneity when applying under the porous occasion, be not easy to block grid, thereby, the electrode for capacitors that obtains when use is as the occasion of the electrode of lithium-ion capacitor, not only lithium doping can be do not hindered, and good electrode activity can be obtained.
More than, example of the present invention is specifically described, example of the present invention has more than and is limited to above-mentioned example, and various variations can be arranged.
[embodiment]
Below, specific embodiments of the invention are described, the present invention is not only limited to these.In following content, the words that " part " and " % " is not particularly limited all are benchmark with the quality.In addition, the mensuration of number average bead diameter is undertaken by aforesaid method equally.
[embodiment 1]
(polymerization process of fluorine type polymer)
To possess carry out nitrogen replacement fully in the autoclave of the about 6L of internal volume of electromagnetic type stirrer after, add the pure water of 2.5L deoxidation and 25g perfluoro decanoate ammonium as emulsifying agent, on one side stir on one side with 350rpm and to be warmed up to 60 ℃.Then, add the mixed gas that 70% vinylidene fluoride (VDF) and 30% hexafluoro propylene (HFP) constitute and reach 20kg/cm until interior pressure 2G.Then, use nitrogen to be pressed into the fluorocarbon that contain 20% di-isopropyl peroxydicarbonate 113 solution of 25g, the beginning polymerization as polymerization starter.In order to make the interior pressure in the polymerization remain on 20kg/cm 2G is pressed into the mixed gas that is made of 60.2%VDF and 39.8%HFP successively.And, along with polymeric progress,, after 3 hours, use nitrogen to be pressed into and the polymerization starter of isodose before because polymerization velocity descends, continue reaction 3 hours again.Thereafter, cooling stops to stir reaction solution the time, emits unreacted monomer, and reaction is stopped, and obtains containing the emulsion [A] of the microparticle [A] that fluorine type polymer constitutes.The number average bead diameter of the microparticle [A] that fluorine type polymer constitutes is 120nm.From 19Each monomeric quality ratio of components that F-NMR tries to achieve is VdF/HFP=85/15.
(polymerization process of (methyl) acrylic polymers)
After carrying out nitrogen replacement fully in the removable flask of capacity 7L, add emulsion [A], 0.1 part of polymerizability emulsifying agent " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 9 parts of methyl methacrylates (MMA), 0.4 part of vinylformic acid (AA) and 170 parts of water that 10 parts (solids component conversions) obtain, drop into 0.3 part of Potassium Persulphate and 0.1 part of S-WAT as polymerization starter, reacted 2 hours down at 50 ℃.
On the other hand, 80 parts of water of input, 0.5 part " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 54 parts of 2-EHAs (2EHA), 17 parts of methyl methacrylates, 9 parts of vinylbenzene (ST) and 0.6 part of vinylformic acid mix in other container, and emulsification obtains emulsion equably.This emulsion is put into the removable flask of front, 50 ℃ of reactions 3 hours down, again 80 ℃ of reactions 1 hour down.Then, cooling stops reaction, and regulating pH with sodium hydroxide solution is 7, drops into 0.05 part of " NOPCO NXZ " (manufacturing of SAN NOPCO company) as defoamer, obtains containing the water dispersion medium [1] of polymer beads [1] thus.
The number average bead diameter of the polymer beads [1] in the water dispersion medium that obtains [1] is 200nm.
[embodiment 2]
(polymerization process of fluorine type polymer)
To possess carry out nitrogen replacement fully in the autoclave of the about 6L of internal volume of electromagnetic type stirrer after, add the pure water of 2.5L deoxidation and 50g perfluoro decanoate ammonium as emulsifying agent, on one side stir on one side with 350rpm and to be warmed up to 60 ℃.Then, add the mixed gas that 70% vinylidene fluoride (VDF) and 30% hexafluoro propylene (HFP) constitute and reach 20kg/cm until interior pressure 2G.Then, use nitrogen to be pressed into the fluorocarbon that contain 20% di-isopropyl peroxydicarbonate 113 solution of 25g, the beginning polymerization as polymerization starter.In order to make the interior pressure in the polymerization remain on 20kg/cm 2G is pressed into the mixed gas that is made of 60.2%VDF and 39.8%HFP successively.And, according to polymeric progress,, after 3 hours, use nitrogen to be pressed into and the polymerization starter of isodose before because polymerization velocity descends, continue reaction 3 hours again.Thereafter, cooling reaction solution, and stop to stir is emitted unreacted monomer, and reaction is stopped, and obtains containing the emulsion [B] of the microparticle [B] that fluorine type polymer constitutes.The number average bead diameter of the microparticle [B] that fluorine type polymer constitutes is 75nm.From 19Each monomeric quality ratio of components that F-NMR tries to achieve is VdF/HFP=85/15.
Except using emulsion [B] replacement emulsion [A], other polymerization process with (methyl) acrylic polymers of embodiment 1 is identical, obtains containing the water dispersion medium [2] of polymer beads [2].
The number average bead diameter of the polymer beads [2] in the water dispersion medium that obtains [2] is 120nm.
[embodiment 3～5]
Except according to such use the polymerizable monomer as shown in table 1 below, other is identical with embodiment 1, obtains water dispersion medium [3]～[5].
Separately the number average bead diameter of polymer beads [3]～[5] is illustrated in the table 1 in the water dispersion medium that obtains [3]～[5].
[embodiment 6]
(polymerization process of fluorine type polymer)
To possess carry out nitrogen replacement fully in the autoclave of the about 6L of internal volume of electromagnetic type stirrer after, add the pure water of 2.5L deoxidation and 25g perfluoro decanoate ammonium as emulsifying agent, on one side stir on one side with 350rpm and to be warmed up to 60 ℃.Then, add the mixed gas that 45% vinylidene fluoride (VDF) and 55% hexafluoro propylene (HFP) constitute and reach 20kg/cm until interior pressure 2G.Then, use nitrogen to be pressed into the fluorocarbon that contain 20% di-isopropyl peroxydicarbonate 113 solution of 25g, the beginning polymerization as polymerization starter.In order to make the interior pressure in the polymerization remain on 20kg/cm 2G is pressed into the mixed gas that is made of 60.2%VDF and 39.8%HFP successively.And, according to polymeric progress,, after 3 hours, use nitrogen to be pressed into and the polymerization starter of isodose before because polymerization velocity descends, continue reaction 3 hours again.Thereafter, cooling reaction solution, and stop to stir is emitted unreacted monomer, and reaction is stopped, and obtains containing the emulsion [C] of the microparticle [C] that fluorine type polymer constitutes.The number average bead diameter of the microparticle [C] that fluorine type polymer constitutes is 120nm.From 19Each monomeric quality ratio of components that F-NMR tries to achieve is VdF/HFP=60/40.
(polymerization process of (methyl) acrylic polymers)
After carrying out nitrogen replacement fully in the removable flask of capacity 7L, add emulsion [C], 0.1 part of polymerizability emulsifying agent " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 9 parts of methyl methacrylates, 0.4 part of vinylformic acid and 170 parts of water that 10 parts (being scaled solids component) obtains, drop into 0.3 part of Potassium Persulphate and 0.1 part of S-WAT as polymerization starter, reacted 2 hours down at 50 ℃.
On the other hand, drop into 80 parts of water, 0.5 part " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 54 parts of 2-EHAs, 17 parts of methyl methacrylates, 9 parts of vinylbenzene and 0.6 part of vinylformic acid and mix in other container, emulsification obtains emulsion equably.This emulsion is put into the removable flask of front, 50 ℃ of reactions 3 hours down, again 80 ℃ of reactions 1 hour down.Then, cooling stops reaction, and regulating pH with sodium hydroxide solution is 7, drops into 0.05 part of " NOPCO NXZ " (manufacturing of SAN NOPCO company) as defoamer, obtains containing the water dispersion medium [6] of polymer beads [6] thus.
The number average bead diameter of the polymer beads [6] in the water dispersion medium that obtains [6] is 200nm.
[comparative example 1]
(polymerization process of fluorine type polymer)
To possess carry out nitrogen replacement fully in the autoclave of the about 6L of internal volume of electromagnetic type stirrer after, add the pure water of 2.5L deoxidation and 15g perfluoro decanoate ammonium as emulsifying agent, on one side stir on one side with 350rpm and to be warmed up to 60 ℃.Then, add the mixed gas that 44.2% vinylidene fluoride (VDF) and 55.8% hexafluoro propylene (HFP) constitute and reach 20kg/cm until interior pressure 2G.Then, use nitrogen to be pressed into the fluorocarbon that contain 20% di-isopropyl peroxydicarbonate 113 solution of 25g, the beginning polymerization as polymerization starter.In order to make the interior pressure in the polymerization remain on 20kg/cm 2G is pressed into the mixed gas that is made of 60.2%VDF and 39.8%HFP successively.And, according to polymeric progress,, after 3 hours, use nitrogen to be pressed into and the polymerization starter of isodose before because polymerization velocity descends, continue reaction 3 hours again.Thereafter, cooling reaction solution, and stop to stir is emitted unreacted monomer, and reaction is stopped, and obtains containing the emulsion [D] of the microparticle [D] that fluorine type polymer constitutes.The number average bead diameter of the microparticle [D] that fluorine type polymer constitutes is 200nm.From 19Each monomeric quality ratio of components that F-NMR tries to achieve is VdF/HFP=85/15.
(polymerization process of (methyl) acrylic polymers)
After carrying out nitrogen replacement fully in the removable flask of capacity 7L, add emulsion [D], 0.1 part of polymerizability emulsifying agent " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 9 parts of methyl methacrylates, 0.4 part of vinylformic acid and 170 parts of water that 10 parts (solids component conversions) obtain, drop into 0.3 part of Potassium Persulphate and 0.1 part of S-WAT as polymerization starter, reacted 2 hours down at 50 ℃.
On the other hand, drop into 80 parts of water, 0.5 part " ADEKAREASOAP SR1025 " (rising sun electrification company makes), 54 parts of 2-EHAs, 16 parts of methyl methacrylates, 9 parts of vinylbenzene and 1.6 parts of vinylformic acid and mix in other container, emulsification obtains emulsion equably.This emulsion is put into the removable flask of front, 50 ℃ of reactions 3 hours down, again 80 ℃ of reactions 1 hour down.Then, cooling stops reaction, and regulating pH with sodium hydroxide solution is 7, drops into 0.05 part of " NOPCO NXZ " (manufacturing of SAN NOPCO company) as defoamer, obtains containing the water dispersion medium [7] of polymer beads [7] thus.
The number average bead diameter of the polymer beads [7] in the water dispersion medium that obtains [7] is 420nm.
[comparative example 2～4]
Except according to such use the polymerizable monomer as shown in table 1 below, other is identical with embodiment 1, obtains water dispersion medium [8]～[10].
Separately the number average bead diameter of polymer beads [8]～[10] is illustrated in the table 1 in the water dispersion medium that obtains [8]～[10].
[evaluation]
(1) adhesivity between evaluation collector and the electrode layer
(1-1) make the electrode of estimating usefulness
Adding ion exchanged water in 100 parts of gacs " Network ラ レ コ one Le YP " (manufacturing of Network ラ レ ケ ミ カ Le company), 5 parts of conductive carbon " デ Application カ Block ラ Star Network " (Denki Kagaku Kogyo kabushiki's manufacturing), 3 parts of carboxymethyl celluloses (manufacturing of ダ イ セ Le chemical company) and 5 parts of water dispersion mediums [1]～[10] stirs, make its slurries solid component concentration form 25%, modulate the electrode slurries of uniform evaluation usefulness thus.Then, by scraping the skill in using a kitchen knife in cookery electrode of synthetic evaluation usefulness is coated on the aluminium foil surface of thickness 20 μ m equably with slurries.Use drying machine after dry 15 minutes down at 120 ℃, re-use Vacuumdrier 5mmHg, 150 ℃ of following drying under reduced pressure 2 hours, obtain having formed electrode [1]～[10] of the evaluation usefulness of the electrode layer that on the one side of the collector that aluminium foil constitutes, contains gac thus.
(1-2) evaluation experimental
Electrode [1]～[10] of above-mentioned evaluation usefulness are cut into the experiment slice of wide 2cm * long 10cm, use double sticky tape that the surface of electrode layer one side of this experiment slice is attached on the aluminium sheet, on the other hand, on the surface of collector one side of experiment slice, attach the adhesive tape " セ ロ テ one プ (registered trademark) " (manufacturing of ニ チ バ Application company) (JIS Z1522 regulation) of wide 18mm, measure 5 speed with 50mm/min intensity (g/cm) during stripping tape on 90 ° of directions, calculate its mean value as stripping strength (g/cm).Its result is shown in the table 1.
The value of stripping strength is big more, and the adhesion strength between collector and the electrode layer is big more, can make the evaluation that is difficult to the stripping electrode layer from collector.
(2) to the coating of the collector of grid structure
100 parts of gacs " Network ラ レ コ one Le YP " (manufacturing of Network ラ レ ケ ミ カ Le company), 5 parts of conductive carbon " デ Application カ Block ラ Star Network " (Denki Kagaku Kogyo kabushiki's manufacturing), adding ion exchanged water in 3 parts of carboxymethyl celluloses (manufacturing of ダ イ セ Le chemical company) and 5 parts of water dispersion mediums [1]～[10] stirs, make its slurries solid component concentration form 25%, thus the paste 200cc that modulates is joined the paste bottom-dump bank portion of the The coating experiment device " ModelEPUF-2010 " of weaving cotton cloth, to the nickel system wire netting " LW 10 " of wide 100mm (Japanese metal industry company make) with draw speed 0.5m/min, the mode of blade gap 0.25mm applies.Then, use dry 15 minutes of drying machine down at 120 ℃, and then by using observation by light microscope with the material of Vacuumdrier after 5mmHg, 150 ℃ of following drying under reduced pressure 2 hours, calculate in 200 grids arbitrarily, block the ratio (%) of the metal mesh of grid.
The ratio of blocking mesh is more little, can not make and can stop up the metal mesh, and have the evaluation of good coating.
(table 1)
Figure A20091013263100241
As shown in table 1, the water dispersion medium in the embodiment of the invention 1～6 is compared with comparative example 1～4, obviously can manufacturing and the adhesivity of collector and electrode layer and to all good electrode of coating of the collector of grid structure.
Combination for capacitor electrode adhesive of the present invention can be used as the tackiness agent that obtains electrode for capacitors and uses, and its electrode for capacitors is applicable to the electrical condenser of double charge layer capacitor, lithium-ion capacitor etc.

Claims (7)

1. combination for capacitor electrode adhesive, it is characterized in that containing polymer composition (A) and dispersion medium (B), this polymer composition (A) is by (a) composition: fluorine type polymer 5～20 quality % and (b) composition: monomer structure unitary (methyl) acrylic polymers 80～95 quality % that contain from following general formula (1) expression constitute, it is the granular polymer composition of number average bead diameter 0.1～0.4 μ m
General formula (1) CH 2=CR 1COOR 2
In above-mentioned general formula (1), R 1Expression hydrogen atom or methyl, R 2The alkyl or cycloalkyl of expression carbonatoms 1～18.
2. the described combination for capacitor electrode adhesive of claim 1, the fluorine type polymer that it is characterized in that above-mentioned (a) composition contains the structural unit of 80～95 quality % from vinylidene with respect to whole 100 quality % of described fluorine type polymer.
3. claim 1 or 2 described combination for capacitor electrode adhesive, (methyl) acrylic polymers that it is characterized in that above-mentioned (b) composition contains the structural unit of 10～35 quality % from methyl methacrylate with respect to whole 100 quality % of described (methyl) acrylic polymers.
4. claim 1 or 2 described combination for capacitor electrode adhesive is characterized in that the structure after above-mentioned polymer composition has above-mentioned (a) composition and compoundization of above-mentioned (b) composition.
5. the described combination for capacitor electrode adhesive of claim 4, it is characterized in that above-mentioned polymer composition be by the granule that constitutes with (a) composition as nucleus, use the monomer of above-mentioned general formula (1) expression to carry out the nucleus polymerization and form.
6. electrode for capacitors slurries is characterized in that containing described combination for capacitor electrode adhesive of claim 1 and electrode active material.
7. electrode for capacitors is characterized in that adopting the described electrode for capacitors of claim 6 to be coated on collector with slurries and drying makes.
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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