CN101486839A - Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer - Google Patents

Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer Download PDF

Info

Publication number
CN101486839A
CN101486839A CNA2008100491101A CN200810049110A CN101486839A CN 101486839 A CN101486839 A CN 101486839A CN A2008100491101 A CNA2008100491101 A CN A2008100491101A CN 200810049110 A CN200810049110 A CN 200810049110A CN 101486839 A CN101486839 A CN 101486839A
Authority
CN
China
Prior art keywords
acid
solid electrolyte
poly
compound
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008100491101A
Other languages
Chinese (zh)
Other versions
CN101486839B (en
Inventor
宁俊禄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHENGZHOU TAIDA ELECTRONIC MATERIAL TECHNOLOGY Co Ltd
Original Assignee
ZHENGZHOU TAIDA ELECTRONIC MATERIAL TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHENGZHOU TAIDA ELECTRONIC MATERIAL TECHNOLOGY Co Ltd filed Critical ZHENGZHOU TAIDA ELECTRONIC MATERIAL TECHNOLOGY Co Ltd
Priority to CN2008100491101A priority Critical patent/CN101486839B/en
Publication of CN101486839A publication Critical patent/CN101486839A/en
Application granted granted Critical
Publication of CN101486839B publication Critical patent/CN101486839B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

An electroconductive polymer compound contains electroconductive high molecules, polyanion and aromatic compound with at least one functional group of alkoxide, nitryl and amino. The electroconductive polymer compound has high conductivity and can even maintain the high conductivity in high temperature environment. In the solid electrolyte layers of a solid electrolytic capacitor, at least one layer contains electroconductive high molecules, polyanion and aromatic compound that has at least one functional group of alkoxide, nitryl and amino. The capacitor has excellent ESR property and stability in high temperature condition.

Description

Conductive polymer composition, solid electrolyte and the solid electrolytic capacitor that uses this solid electrolyte
Technical field
The present invention relates to conductive polymer composition, and be used for the solid electrolyte of solid electrolytic capacitor (electrolytic capacitor) and use the solid electrolytic capacitor and the surface-mounted transmission line element of this solid electrolyte.
Background technology
The conductive polymer composition that comprises electroconductive polymer is expected to be applied to: conductive applications, electrically conducting coating, antistatic agent, electromagnetic shielding material, transparency electro-conductive material, battery material, capacitor material, transmitter, electronic material, semiconductive material, electrostatic duplicating parts, transfer member, solar cell, Organic Light Emitting Diode, field emission type display (FED), touch-screen, EL sheet (Electroluminance), OTFT (Organic thin-film transistor), Electronic Paper (epaper), electrofax material etc.
In recent years, along with the digitizing of electronic machine, require to reduce of the impedance of employed electrical condenser gradually at high-frequency region.For adapting to this requirement, used gradually and had for example by aluminium, tantalum (Ta), the anode that the metal porous body of niobium valve actions such as (Nb) constitutes, the dielectric oxide film that constitutes by the metal oxide film of described valve action, on this oxide film, form electroconductive polymer layer then as solid electrolyte, carbon-coating, and the formed negative electrode of silver layer obtains.
As the electroconductive polymer layer of the solid electrolyte of this functional electric container, use the pyrroles, thiophene, aniline etc. are as monomer.When the electroconductive polymer that forms as the electrical condenser solid electrolyte, the main chemical oxidative polymerization method that uses, this method is by adding oxygenant and doping agent in electroconductive polymer, on the oxide film of metal porous body, induce reaction and form electroconductive polymer layer (referring to patent documentation 1, for example Japanese Unexamined Patent Application publication spy opens flat 05-166681).
On the other hand, also use following technology: on the oxide film of metal porous body, do not carry out polymerization, but by preparing the soluble conductive macromolecular solution independently, flood this conductive-polymer solution and enter metal porous body, be dried to then and film, thereby on oxide film, form electroconductive polymer layer (referring to patent documentation 2, for example Japanese Unexamined Patent Application discloses 2001-023437).
In the technology of patent documentation 2, the high molecular molecular weight of soluble conductive enters porous insert inside with it perviousness is generally inverse relation, and the resistance of filming and the molecular weight of electroconductive polymer then tend to proportional.Therefore, if only form the solid electrolyte of electrical condenser with the soluble conductive macromolecular solution, then the ESR of electrical condenser and electric capacity have both and select one relation, and therefore the example that uses seldom.
Usually take following method to use the soluble conductive macromolecular solution:
(1) although its perviousness that enters porous insert is low, the soluble conductive polymer that molecular weight is big is used to prepare and can forms the soluble conductive macromolecular solution with low-resistance electroconductive polymer layer, thereby forms thicker electroconductive polymer layer near being combined in the outermost surface of porous insert with chemical oxidative polymerization method.
(2) although its resistance height, the soluble conductive polymer that molecular weight is little is used to prepare even also can promote in porous insert inside the soluble conductive macromolecular solution of electroconductive polymer layer formation, thereby combines polymer layer as the matrix in the electrolytic polymerization with the electrolytic polymerization method.
3,4-ethene dioxythiophene (below be called " EDOT ") is oneself monomer through beginning to be used widely, and the big characteristics of one can obtain the low resistance electroconductive polymer exactly, therefore, when " EDOT " is used for the soluble conductive polymer, the normal using method that is similar to (1) of using.Now, when using the method for similar (1), compare with the electroconductive polymer that only forms by chemical oxidising polymerisation, the electroconductive polymer that is formed by the soluble conductive macromolecular solution can only form has several times to 100 times or the polymer layer of high resistivity more, in addition, its stability at high temperature is also poor, and resistance can raise at short notice, and using in solid electrolytic capacitor is a subject matter.
Usually, so-called electroconductive polymer is the polypyrrole class, polythiophene class, and the polyacetylene class, poly-inferior benzene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound, the metaldehyde class, poly-vinylene thiophene-based, and these multipolymer etc.These electroconductive polymers can be by chemical oxidative polymerization and the preparation of electrolytic polymerization method.
The electrolytic polymerization method is in the ionogen mixing solutions formed of the monomer of electroconductive polymer and doping agent, adds ready-made electrode materials, forms the film of electroconductive polymer on electrode.Therefore, be difficult to preparation in large quantities.
In contrast to this, in chemical oxidative polymerization, do not have such restriction, the monomer of electroconductive polymer and suitable oxygenant and catalyzer, can be in solution a large amount of electroconductive polymer of polymerization.But, in chemical oxidative polymerization, along with the growth of electroconductive polymer main chain, for the solvability reduction of organic solvent.Therefore, what obtain mostly is insoluble solid shape powder, therefore, is difficult to use with this state.
For addressing this problem, following scheme has been proposed: by importing suitable substituting group or increasing the solvability of organic solvent with the polyanion based compound.As the high molecular example of soluble conductive, the Baytron-P of H.C.Starck-VTECHLtd. production etc. is arranged on market.Yet this electroconductive polymer has high resistance and resistance enlarges markedly under high-temperature problem.
Summary of the invention
The present invention mainly solves the high resistance of electroconductive polymer and the problem that resistance enlarges markedly under high-temperature.And the performance of the solid electrolytic capacitor of solution use electroconductive polymer, and the performance that solves under the hot environment is hanged down inferior problem.
The present invention provides a kind of conductive polymer composition that can obtain to film, and this films is to have the resistivity of reducing, and also can keep low-resistivity under hot environment.
Conductive polymer composition of the present invention is to have electroconductive polymer and polyanion, and contains-oxyl, nitro, and the aromatics of at least a functional group in the amino is formed.
In the conductive polymer composition of the present invention, can also contain doping agent, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound.
Another object of the present invention is by using filming of above-mentioned conductive polymer composition, a kind of circuit card that has the solid electrolytic capacitor of excellent ESR property and use this solid electrolytic capacitor being provided.And under hot environment, also can keep the performance of solid electrolytic capacitor.
One deck at least in the solid electrolyte layer of solid electrolytic capacitor of the present invention comprises electroconductive polymer and polyanion, and contains-oxyl, nitro, the aromatics of at least a functional group in the amino.Also contain carboxyl in the aromatics, hydroxyl, cyano group, sulfonic group, carbonyl, amide group, ester group, at least a functional group in fluorine-based.
Can also contain doping agent in the solid electrolyte layer, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound.
Conductive polymer composition in the present invention can obtain having high conductivity, the excellent in stability of the relative outside atmosphere of specific conductivity, and thermotolerance, advantages such as permanent stability.
Solid electrolytic capacitor of the present invention, the solid electrolytic capacitor that can obtain having excellent ESR property.And under hot environment, also can keep the performance of solid electrolytic capacitor.
Embodiment
Below, use example of the present invention is described.But the present invention is not limited to following each example.For example, the integrant of these examples and mode correspondence or appropriate combination mutually to each other.
Conductive polymer composition of the present invention is to have electroconductive polymer and polyanion, and contains-oxyl, nitro, and the aromatics of at least a functional group in the amino is formed.Can add doping agent as required, resinous principle is arranged, electroconductibility is adjusted agent, conductive particle, ionic conductivity compound, ionic compound, dispersion agent, bridging agent etc.
(electroconductive polymer)
So long as main chain is got final product by the organic polymer that common rail system constitutes, there is not particular restriction as electroconductive polymer of the present invention.For example: polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyacetylene class and derivative thereof, poly-inferior benzene class and derivative thereof, polyphenylene 1, inferior vinyl of 2-and derivative thereof, polyaniline compound and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, and these multipolymer etc.Especially from keeping chemical stabilization aloft, operability is good etc., and the aspect is considered, preferably uses polypyrrole class, polythiophene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound.
As the object lesson of the electroconductive polymer of preferred use as polypyrrole, poly-(3-methyl) pyrroles, poly-(3-carboxyl) pyrroles, poly-(3-methyl-4-propyloic) pyrroles, poly-(3-methoxyl group) pyrroles, poly-(3-hexyloxy) pyrroles, poly-(3-methyl-4-hexyloxy) pyrroles waits the polypyrrole class; Polythiophene, poly-(3-methyl) thiophene, poly-(3-hexyl) thiophene, poly-(3-hydroxyl) thiophene, poly-(3-methoxyl group) thiophene, poly-(3-hexyloxy) thiophene, poly-(3-octyloxy) thiophene, poly-(3-oxygen in last of the ten Heavenly stems base) thiophene, poly-(3-dodecyloxy) thiophene, poly-(3, the 4-dihydroxyl) thiophene, poly-(3, the 4-dimethoxy) poly-(3, the 4-diethoxy) thiophene thiophene),, poly-(3,4-two hexyloxy) thiophene, poly-(3,4-oxygen base in two heptan) thiophene, poly-(3,4-two octyloxies) thiophene, poly-(3,4-didecyl oxygen base) thiophene, poly-(3,4-docosane oxygen base) thiophene, poly-(3, the 4-ethylenedioxy) thiophene, poly-(3, the inferior third dioxy base of 4-) thiophene, poly-(3,4-butylene dihydroxyl) thiophene, poly-(3-methyl-4-methoxyl group) thiophene, poly-(3, the 4-ethylene dioxy) thiophene, polythiophene class such as poly-(3,4-butylene dioxy) thiophene; And polyaniline, poly-(2-aminotoluene), poly-(3-isobutyl-aniline), poly-(2-aniline sulfonic acid), poly-polyaniline compounds such as (3-aniline sulfonic acid) etc.
Electroconductive polymer can prepare by chemical oxidative polymerization.Under the condition that has oxygenant or catalyzer, change into electroconductive polymer from polymerisable electroconductive polymer free oxygen.As long as having more than 2, the polymeric unit of electroconductive polymer can obtain good electrical conductivity.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as oxygenant, iron(ic) chloride (III), ferric sulfate (III), cupric chloride (II), tosic acid iron transistion metal compounds such as (III), silver suboxide, Cs2O metal oxides such as (Se), hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen etc.
As the solvent of chemical oxidising polymerisation, so long as solubilized or disperse oxygenant or the solvent of oxypolymerization catalyzer gets final product, for example: water, N-Methyl pyrrolidone (NMP), N, N '-dimethyl methyl phthalein amine (DMF), N, N '-dimethyl second phthalein amine (DMAc), dimethyl sulfoxide (DMSO) (DMSO), methylphenol, phenol, xylenol, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, hexane, benzene, toluene, formic acid, acetate, ethylene carbonate vinegar, propylene carbonate vinegar, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, acetonitrile, methoxyacetonitrile, propionitrile, benzene nitrile, glycol, glycerine, triethylene glycol butyl ether triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether etc.As required, these solvents can be independent, two or more mixing, or mix use with other organic solvents.
As polymerization temperature, need only scope at-30～200 ℃, be preferable over 0～130 ℃.
Electroconductive polymer of the present invention can be at oxygenant, carries out chemical oxidising polymerisation under the existence of catalyzer and polyanion.The polymeric electroconductive polymer can obtain good solubility and electroconductibility under the polyanion containing.
As polyanion so long as side chain has the carboxylic acid group, sulfonic group, sulfate, the polymer of phosphate can use.For example can enumerate as main chain: the polyalkylene compound that main chain is made of repeatedly methylene radical, main chain contain the poly-alkenylene compound of the component unit formation of vinyl, poly-vinegar resin, poly-phthalein polyimide resin, poly-phthalimide resin, fluoro-resin, ethenoid resin, Resins, epoxy, xylene resin, the aramid resin, polyurethane is a resin, melmac, phenolic resin, polyethers, acrylic resin and these compositions such as copolymer resins.Polyanion can be that polymerizable monomer and carboxylic acid are that polymerizable monomer obtains with polymerization by sulfonic acid, also can get multipolymer with other polymerizable monomers as required.As concrete example as: replace or unsubstituted vinyl sulfonic acid compound, replace or unsubstituted styrene sulfonic acid compound, replace or unsubstituted heterocycle sulfoacid compound, replace or unsubstituted propylene phthalein amine sulfoacid compound, replace or the inferior vinyl sulfonic acid compound of unsubstituted ring, replace or unsubstituted vinyl aromatic sulfoacid compound replacement or unsubstituted vinylformic acid etc.Can enumerate as other polymerizable monomers: replace or unsubstituted vinyl compound, the substitutional crylic acid compound, replace or unsubstituted vinylbenzene, replace or unsubstituted vinyl-amine, the heterogeneous ring compound that contains unsaturated group, replace or unsubstituted propylene phthalein amine compound, replace or unsubstituted ring vinylidene compound, replace or unsubstituted adiene cpd, replace or unsubstituted vinyl aromatic compound, replace or unsubstituted divinyl benzene compound substituted ethylene base oxybenzene compound, replace silyl vinylbenzene arbitrarily, arbitrarily 5-substituted phenol compounds etc.
Can use peroxydisulfate such as ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate as polymerizing catalyst and oxygenant, iron(ic) chloride (III), ferric sulfate (III), cupric chloride (II), tosic acid iron transistion metal compounds such as (III), silver suboxide, metal oxides such as Cs2O, hydrogen peroxide, superoxide such as ozone, organo-peroxides such as peroxidation benzene first phthalein, oxygen, photopolymerization catalyzer etc.
The object lesson of polyanion can be enumerated: polyvinyl sulfonic acid with and salt, polystyrolsulfon acid with and salt, the polyacrylic acid vinyl sulfonic acid with and salt, poly-first for allyl sulfonic acid with and salt, poly-methyl allyloxy Phenylsulfonic acid with and salt, poly-sulfonic acid vinegar resin with and salt, poly-sulfonic acid phthalimide resin with and salt etc.
As the positively charged ion of polyanionic salt for example: ammonium salt, tetramethyl ammonium, tetraethyl-ammonium salt, the tetrapropyl ammonium salt, 4-butyl ammonium, tetrahexyl ammonium salt, trimethylammonium ethyl ammonium salt, the trimethylphenyl ammonium salt, triethyl phenyl ammonium salt, Three methyl Benzene idol phthalein ammonium salt, 4 grades of ammonium salts such as trimethylammonium octyl group ammonium salt, metal cation salt, imidazole-like ionic salt, pyridines ion salt etc.
The molecular-weight average of polyanion is 1,000～1,000,000 scope, preferred 5,000～800,000.
The mass ratio of polyanion and electroconductive polymer (polyanion: electroconductive polymer) preferred 99:1～1:99, more preferably 95:5～10:90, most preferably 80:20～30:70.As long as in this scope, then electroconductibility and solvent solubility are all high, when polyanion is lower than this scope, the inadequate tendency of solvent solubility are arranged then.When mass ratio is higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(aromatics)
As long as aromatics of the present invention is to contain-oxyl on the aromatic ring, nitro, a kind of the getting final product in the amino all do not have particular restriction to aromatic ring and other functional group.For example can contain carboxyl, hydroxyl, cyano group, sulfonic group, carbonyl, amide group, ester group, at least a functional group in fluorine-based.As aromatic ring benzene class for example, naphthalene class, acene class, pyroles, thiophene-based, imidazoles, pyridines etc.From electroconductibility and the preferred benzene class of system film, naphthalene class, acene class.Specifically can enumerate: oil of mirbane, Ortho Nitro Toluene, 1-oil of mirbane propane, p-Nitrophenyl chloride, oil of mirbane ethane, p-fluoronitrobenzene, 2,5-dichloronitrobenzene, 3-nitro-4-chlorine tert.-butylbenzene, 2 nitro biphenyl, N-methyl-p-nitroaniline, 2-methyl-3-nitro phenylformic acid, 2-methyl-4-nitrobenzoic acid, 2, the 4-difluoro nitrobenzene, the 3-nitrophenols, 4-nitrophenols, 4-nitrophenol sodium salt, adjacent nitro p-methyl phenol, 2-chloro-4-nitrophenol, m-nitrophenol, 2,2, 4-dinitrophenol, 2-amino-4-nitrophenols, 2-amino-4-nitrophenols list sodium salt, 2,4-dimethoxy-1-oil of mirbane, 2,5-dimethoxy oil of mirbane, 2,6-dimethoxy oil of mirbane, 2,5-diethoxy oil of mirbane, para-nitrochloro-benzene, m-nitrobenzene sulfonic acid, p-Nitroaniline, 3,4-dimethoxy oil of mirbane, 1,2-dimethoxy-4 '-oil of mirbane, 2,4-dinitrobenzene methyl ether 2,4-Dinitroanisole, 4-amino-3-Nitroanisole 4-Methoxy-2-nitroaniline, 4-chloro-3-Nitroanisole, 4-methoxyl group-2-nitrophenols (4-methoxy-2-nitrophenol), the 4-nitronaphthol, 2,4-dinitrobenzene naphthols, 1,2-dimethoxy benzene (dimethoxybenzen), 2-nitro-4,5-dimethoxybenzoic acid, 2-Nitro-4,5-dimethoxy-benzoic acid, 3,4-dimethoxy-6-aminobenzaldehyde 3,4-Dimethoxy-6-aminobenzaldehyde, 3,5-dimethoxy-4 '-hydroxybenzene 3,5-Dimethoxy-4-Hydroxybenzoate, 5,6-dimethoxy-2-(4-pyridyl) methylene radical-1-indone 5,6-dimethoxy-2-(pyridine-4-yl) methylene-indan-l-one, 3,4-dimethoxy-acetophenone 3,4-Dimethoxy Acetophenone, 2-amino-4,6-dimethoxypyridin 2-amino-4,6-dimethoxy pyrimidine, 2,5-dimethoxyaniline 2,5-dimethoxy aniline, 1,2-dimethoxy benzene 1,2-dimethoxybenzene, 1,2,4-trimethoxy-benzene Trimethoxy benzene, 2,4,6-trimethoxybenzoic acid trimethoxy benzoic acid, 1,2,3-trimethoxy-benzene 1,2,3-Trimethoxy Benzene, 2,3,4-TMB (ケ ト Application), 3,4,5-TMB, 2,3, the 4-trimethoxybenzoic acid, Tenox PG (エ ス テ Le), Stabilizer GA 8, Progallin A, Weibull, Weibull, 3,4,5-tri-methoxybenzoate (エ ス テ Le), 2,3,4-trimethoxybenzoic acid ethyl ester, 2,3,4 trimethoxybenzoic acid propyl ester (エ ス テ Le), 3,4,5-trimethoxy-N-(3-piperidyl) benzamide, 3,5-dimethoxy-4 '-methyl hydroxybenzoate methyl syringate, the 2-phenoxyethyl alcohol, 2-phenoxypropanol, glycol monomethyl phenolic ether, ethylene glycol phenyl ether, 4-anisole methyl alcohol 4-Methoxybenzyl Alcohol, vanillyl alcohol 4-Hydroxy-3-methoxybenzyl alcohol, 2-[4-(2-hydroxyethyl) phenoxy group] ethanol (HQEE) 1,3-Bis (2-hydroxyethoxy) benzene, 3,5-dimethoxyphenylacetic acid, 2,5-dimethoxyphenylacetic acid 3,5-Dimethoxyphenylacetic Acid, 3,5-dimethoxy-4 '-hydroxy-cinnamic acid 3,5-Dimethoxy-4-hydroxycinnamic Acid, 2-hydroxy 3-methoxybenzene formaldehyde 2-Hydroxy-3-methoxybenzaldehyde, 2-hydroxy-5-methyl oxygen benzaldehyde, 3-phenoxy group-1,2-propylene glycol (3-phenoxy-1,2-propanediol), ((methoxy phenoxy) methyl) oxyethane 1-(3-Methoxyphenoxy)-2-propanol, 4-base-3-methoxybenzaldehyde, vanillic acid, 3-methoxyl group-4-hydroxy benzaldehyde, 4-amino-phenol, 6-amino-4-hydroxy-2-naphthene sulfonic acid, 2-amino-4-nitrophenols/2-Amino-4-nitrophenol, 2,4 difluorobenzene amine, the 4-anisidine, 2-methoxyl group-5-amino-phenol 5-Amino-2-methoxyphenol, 4-N-methyl-p-nitroaniline 4-Nitroaniline, 2-amino-phenol, meta-aminophenol, p-aminophenol, the anisidine anisidine, 2,4 difluorobenzene amine etc.
The mass ratio of aromatics and electroconductive polymer (aromatics: electroconductive polymer) preferred 1:99～99:1, more preferably 20:80～90:10, most preferably 30:70～80:20.As long as in this scope, then electroconductibility and solvent solubility are all high, when electroconductibility adjustment wedding agent is lower than this scope, then can not obtain the tendency of sufficient electroconductibility and film-forming properties sometimes.When mass ratio is higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(doping agent, electroconductibility is adjusted agent)
In order to improve electroconductive polymer and electroconductibility thereof, can the mixing and doping agent, electroconductibility is adjusted agent.Electroconductibility is adjusted the performance that film-forming properties is adjusted in agent in addition.
As long as can produce redox reaction with electroconductive polymer, do not limit electron acceptor or electronics and supply and body as doping agent.For example: halogen compound, Lewis acid, protonic acid etc.Can enumerate chlorine, iodine, iodine chloride, fuorine iodine etc. as halogen compound.In addition, can enumerate phosphorus pentafluoride (PF as Lewis acid 5), arsenic pentafluoride (AsF 5), boron trifluoride (BF 3), boron trichloride (BCl 3) etc.In addition, can enumerate as protonic acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoroboric acid, mineral acids such as hydrofluoric acid, organic carboxyl acid, organic acids such as organic sulfonic acid, organic cyanogen compound etc.
Can use in aliphatics as organic carboxyl acid, aromatic series contains one or more carboxylic acid groups' material on the annular aliphatic etc.For example: formic acid, acetate, oxalic acid, M-nitro benzoic acid, phthalic acid, toxilic acid, fumaric acid, propanedioic acid, tartrate, citric acid, lactic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, nitroacetic acid, triphenylacetic acid etc.Also can use the amine salt of these materials, metal-salt.
Can use in aliphatics as organic sulfonic acid, aromatic series, annular aliphatics etc. are gone up in conjunction with one or more sulfonic materials.Can enumerate as organic sulfonic acid: methylsulphonic acid, ethylsulfonic acid, trifluoromethane sulfonic acid, Phenylsulfonic acid, tosic acid, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, 2, the 4-acid dimethyl, the dipropyl Phenylsulfonic acid, 4-aniline sulfonic acid, p-chlorobenzenesulfonic acid, naphthene sulfonic acid, methyl naphthalene sulfonic acid, naphthalene sulfonic acid formaldehyde condensation polymer, the green onion disulfonic acid, butyl green onion disulfonic acid, 1-second phthalein oxygen base-3,6,8-trisulfonic acid, 7-amino-1,3,6-naphthalene trisulfonic acid, o-sulfobenzoic acid, 3,5-disulfonic acid phenylformic acid, sulfophthalic acid, sulfo group pure terephthalic acid, cysteic acid, 5-sulphosalicylic acid etc.Also can use these ammonium salt, metal-salt.
Content as doping agent is the mol ratio (doping agent: electroconductive polymer) preferred 0.1:1～10:1, more preferably 0.5:1～7:1 of electroconductive polymer.When the content of doping agent is lower than this scope, then can not obtain sufficient electroconductibility sometimes.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
Adjust agent as electroconductibility and can use at hydroxy-containing compounds, carboxylated compound (organic acid) (COOH) contains aminocompound, the amino-contained aromatics contains carbonyl (CO) compound, contains the acetify compound, contain ammonia vinegar based compound, contain ether compound, amide compound contains imide compound, contain acrylic compound, contain epoxy compounds, silicon-containing compound, fluorochemicals etc.
For example can enumerate: N-N-methyl-2-2-pyrrolidone N-, N, N '-dimethyl methyl phthalein amine, N, N '-dimethyl second phthalein amine, dimethyl sulfoxide (DMSO), the triethylene glycol butyl ether, triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, butoxy triethylene glycol ether, oxeye alcohol, arabitol, 3-amino-1, the 2-propylene glycol, N.F,USP MANNITOL, glycol, glycol ether, triethylene glycol, poly-glycol, glycerine, Glycerol dimer, Polyglycerine, sorbyl alcohol, tetramethylolmethane, dipentaerythritol, 3-methoxyl group-1, the 2-propylene glycol, allitol, Xylitol, melampyrum, semi-lactosi, pectinose, glucose, monose, disaccharides, polysaccharide, galacturonic acid, glyconic acid, the DL-hydroxy-butanedioic acid, glutinous acid, gulonic acid, different VC acid, oxalic acid, oxysuccinic acid, diacid ammonium, vitamin c class, tartrate, D-dibenzoyl tartaric acid, heptonic acid and these hydrochlorate, glucosamine, dioxane, diethyl ether, dialkyl ether ethylene glycol vinegar, dialkyl ether propylene glycol vinegar, poly-dialkyl ether ethylene glycol vinegar, poly-dialkyl ether propylene glycol vinegar, imidazoles, dihydroxy-benzene, trihydroxybenzene, dihydroxy naphthlene, trihydroxynaphthalene, m-phthalic acid, SO 3 sulfonated m-phthalic acid, sour methyl esters, vinylcarbinol, the ethene imidazoles, V-Pyrol RC, ethene dimethyl sulfoxide (DMSO), vinylpyridine, vinyl cyanide (AN), N hydroxymethyl acrylamide (N-MAM), acrylic acid amides, vinylformic acid hydroxyl phthalein amine (HEAA), vinylformic acid (AA), propylene phthalein amine, N,N-DMAA, the hydroxyethyl acrylamide, Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410, Rocryl 410 (HPMA), vinylformic acid hydroxy butyl ester (HBA), Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), vinyl sulfonic acid and vinyl sulfonate, styrene sulfonic acid and styrene sulfonate, vinylformic acid vinyl sulfonic acid and vinylformic acid vinyl sulfonate, first for allyl sulfonic acid and first for allyl sulfonate, methyl allyloxy Phenylsulfonic acid and methyl allyloxy benzene sulfonate, vinylidenefluoride, R 1216 etc.
Electroconductibility is adjusted mass ratio (the electroconductibility adjustment agent: electroconductive polymer) preferred 1:99～99:1, more preferably 20:80～90:10, most preferably 30:70～80:20 of agent and electroconductive polymer.As long as in this scope, then electroconductibility and solvent solubility are all high, when electroconductibility adjustment wedding agent is lower than this scope, then can not obtain the tendency of sufficient electroconductibility and film-forming properties sometimes.When mass ratio is higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(electroconductive particle)
Electroconductive particle can be added in the conductive polymer composition of the present invention arbitrarily, as electroconductive particle for example: carbon particles, graphite particle, carbon fiber, carbon nanotube, soccerballene (fullerene), copper, nickel, silver, gold, tin, iron, metallicss such as aluminium, metal acidulants particle, steel fiber etc.Wherein preferred use is added can improve electroconductibility on a small quantity, and the carbon fiber of favorable dispersity, graphite particle, carbon nanotube, soccerballene (fullerene).In addition, carbon particles, graphite particle, carbon fiber, the such carbon material of carbon nanotube has reductive action, has the effect of the electroconductive polymer deterioration that anti-block causes.Replaceable any functional group on this carbon material.For example: carbon particles, porous carbon particle, gac, graphite particle, porous graphite, graphite flake (comprising hand chair form armchair and prionodont zigzag), needle-like graphite, graphite carbon dust, carbon fiber, graphite fibre, activated carbon fiber, Single Walled Carbon Nanotube, double-wall carbon nano-tube, multiple-wall carbon nanotube, carbon 40, carbon 60, carbon 70, carbon 74, carbon 76, carbon 78, carbon 82, carbon 84, carbon 78, and these hydroxylates, the carboxylic acid groupization thing, the sulfonic group thing, hydrosulfate, oxide compound etc.
The mass ratio of electroconductive particle and electroconductive polymer (electroconductive particle: electroconductive polymer) preferred 1:99～90:10, more preferably 10:90～80:20.
Conductive polymer composition of the present invention also can contain other compositions as required.For example to adjust film-forming properties, film toughness etc. are purpose, can use other organic resins and other additives simultaneously.As organic resin, as long as electroconductive polymer is held concurrently molten or blending dispersion can be used any thermosetting resin, thermoplastic resin, photo-curable resin relatively.
As its object lesson of resin, for example can enumerate: poly-vinegar resinoid, poly-phthalimide resinoid, poly-phthalein amine resins, poly-fluorine-type resin, polythylene resin, redix, xylene resin, polyethylene glycols, aromatic species polyamide resin, polyurethane is a resin, poly-vein system resin, the melamine resinoid, phenol resin, polyethers, the copolymer resins of acrylic resin and these materials, siliceous class copolymer resins etc.Can add resinous principle arbitrarily in the electroconductive polymer layer of the present invention as required, add content and also be not particularly limited.
As other additives so long as can and electroconductive polymer is held concurrently molten or blending dispersion can be used any defoamer, neutralizing agent, oxidation inhibitor, tensio-active agent, coupling agent, conductive fillers etc. do not have particular restriction.
(ionic conductivity compound/ionic compound)
Conductive polymer composition of the present invention adds ionic conductivity compound and ionic compound.Add the ion transmission energy that ionic conductivity compound and ionic compound can improve conductive polymer composition.
As long as the ionic conductivity compound ability that transmits ionic compound is arranged, does not have particular restriction.For example the hydroxyl compounds contains carboxyl compounds (organic acid), contains amino compound, the amino-contained quasi-aromatic compound, contain ammonia vinegar compounds, contain ether compound, the amide containing compounds, contain acrylic compounds, siliceous compounds, fluorinated compound etc.As using hydroxyl, carboxyl, ether, vinyl, propenyl, acrylic etc.Be preferable over the hydroxyl compounds from the ionic conductivity face, contain ether compound, contain carboxyl compounds, fluorinated compound etc.In addition, can adjust the electroconductibility of ionic compound with the method for adding solvent or additive etc.Do not impose any restrictions at this.
As long as ionic conductivity is arranged, there is not particular restriction as ionic compound.Known low molion compound and macroion compound all can use.Preferably contain carboxylic compound and salt thereof, sulfonic group compound and salt thereof, ionic liquid etc.
As long as ionic conductivity is arranged, there is not particular restriction as ionogen.Known ionogen and polymer electrolyte all can use.For example: carboxylic compound, sulfonic group compound, the organic acid salt of ionic liquid etc., vitriol, the no organic acid salt of hydrochloride etc. etc.
Another object of the present invention is by using filming of above-mentioned conductive polymer composition, a kind of solid electrolytic capacitor with excellent ESR property being provided.And under hot environment, also can keep the performance of solid electrolytic capacitor.
(solid electrolytic capacitor)
Example to solid electrolytic capacitor of the present invention describes below.
It has solid electrolytic capacitor of the present invention: by the anode bodies that metal porous body is made, be formed at the medium layer that constitutes on the described metallic surface, and the solid electrolyte layer between medium layer and the cathode, and cathode,
In the described solid electrolyte layer, have at least one deck to comprise electroconductive polymer and polyanion, and aromatics, this aromatics contains-oxyl, nitro, at least a functional group in the amino.
When solid electrolytic capacitor of the present invention is wound capacitor, possesses electrolytic paper is arranged.Electrolytic paper is located between described medium layer and cathode.
(anode bodies)
Can enumerate as metal: aluminium (Al), tantalum (Ta), niobium (Nb), titanium (Ti), bell (Hf), zirconium (Zr) etc., wherein as the preferred aluminium of the metal of the employed valve action of capacitor anode, tantalum (Ta), niobium (Nb).Can use oxide film or organic dielectric film as the medium layer on the metallic surface.The preparation method of oxide film medium layer: can carry out after etching and processing increases its surface-area aluminium foil, its surface be carried out the method for oxide treatment; And to the tantalum particle, the sintered compact surface of niobium particle is carried out oxide treatment and is made the known methods such as method of its powdered.
(solid electrolyte layer)
The solid electrolyte layer of solid electrolytic capacitor of the present invention, on the medium layer of solid electrolytic capacitor, use pickling process, method such as spraying method or print process coating (coating) electroconductive polymer coating, then with solvent seasoning, on the medium layer surface, form the conducting film that contains electroconductive polymer, obtain solid electrolyte layer.
When solid electrolytic capacitor of the present invention is wound capacitor, also need have electrolytic paper.Electrolytic paper is located between the medium layer and cathode on the described metallic surface.Solid electrolyte layer with solvent seasoning, forms the conducting film that contains electroconductive polymer behind the solid electrolyte solution dipping, obtains solid electrolyte layer.
As the electrical conductor of solid electrolyte layer, can use aforesaid conductive polymer composition.In the aforesaid conductive polymer composition, can also use and contain ionic conductivity compound or ionic compound.As long as ionic conductivity compound and ionic compound ionic conductivity is arranged, does not have particular restriction.The ionogen of known solid electrolytic capacitor and polymer electrolyte all can use.Preferred carboxyl (COOR), sulfonic group compound, poly-glycol, poly-phthalein amine, polyvinyl alcohol, polyvinyl ether, organic salt and inorganic salt, liquid salt etc.
(solid electrolytic paper)
As the solid electrolytic paper of solid electrolytic capacitor of the present invention, can use the solid electrolytic paper of known solid electrolytic capacitor not have particular restriction.
(cathode)
As the cathode of solid electrolytic capacitor of the present invention, can use electroconductive polymer, carbon, silver, aluminium, copper etc.The preparation method can prepare with electrical conductor paper tinsel or coating, does not have particular restriction.
Beneficial effect
The present invention comprises-oxyl, nitro, amino aromatics.And can obtain high conductivity, and advantage and good electrical conductivity polymeric compositions such as high heat resistance and permanent stability.
Another object of the present invention is by using filming of above-mentioned conductive polymer composition, the solid electrolytic capacitor of excellent properties such as a kind of low ESR of having being provided.And under hot environment, also can keep the performance of solid electrolytic capacitor.
(implementation example)
Preparation object lesson to conductive polymer composition of the present invention and solid electrolytic capacitor describes below.The present invention is not only limited to these object lessons.
Embodiment 1
With 3 of 5g, the 4-ethylene dioxythiophene, the Sodium Persulfate of the polystyrolsulfon acid aqueous solution of the 30wt% of 50g (molecular-weight average 7.5 ten thousand) and 10g, the ferric sulfate of 1g (III) is dissolved in the 1000ml water, stirs 18 hours.
Spent ion exchange resin is removed the residual ion in the solution, obtains polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of mazarine 1.5wt%.
The polystyrolsulfon acid of the 1.5wt% of the 5g that obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution after the 4-nitrophenols of 0.05g mixes stirring, carries out drying in 120 ℃ of degree baking ovens, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 2
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, the 4-nitrophenols of 0.15g mix stir after, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 3
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, the 4-methoxyl group of 0.10g-2-nitrophenols mix stir after, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 4
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, 1 of 0.10g, the 2-dimethoxy benzene, 0.5g the polysulfonates mixed with resin of 25wt% stir after, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 5
Polystyrolsulfon acid-poly-(3 with the 1.5wt% of the 5g of embodiment 1 preparation, 4-ethylene dioxy base) the thiophene aqueous solution, the vanillyl alcohol of 0.10g is after the N-N-methyl-2-2-pyrrolidone N-of 0.20g mixes stirring, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 6
Polystyrolsulfon acid-poly-(3 with the 1.5wt% of the 5g of embodiment 1 preparation, 4-ethylene dioxy base) the thiophene aqueous solution, the 2-[4-of 0.1g (2-hydroxyethyl) phenoxy group] ethanol (HQEE), after mixing is stirred, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 7
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, 3,4 of 0.05g, 5-tri-methoxybenzoate mix stir after, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Embodiment 8
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, the 2-amino of 0.1g-4-nitrophenols mix stir after, in 120 ℃ of degree baking ovens, carry out drying, obtain conductive coating.Estimate the specific conductivity of conductive coating, its result is as shown in table 1.
Comparative example 1
Have only the same method evaluation with polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation and embodiment 1, its result is as shown in table 1.
Table 1
Initial stage specific conductivity (S/cm) 120 ℃ of specific conductivity (S/cm) after 300 hours
Embodiment 1 420 407
Embodiment 2 570 556
Embodiment 3 300 280
Embodiment 4 400 380
Embodiment 5 350 320
Embodiment 6 550 545
Embodiment 7 300 276
Embodiment 8 30 15
Comparative example 1 3.2 0.5
Embodiment 9
(preparation of winding capacitance work in-process sub-prime)
With the anode foils that changes into processing of guide pin on the fourth, the negative foil roll coiled specification 4V-470 μ F winding capacitance work in-process sub-prime of guide pin on solid electrolytic paper and the fourth.
(preparation of solid electrolyte solution)
With 3 of 5g, the 4-ethylene dioxythiophene, the polystyrolsulfon acid aqueous solution of the 3wt% of 500g and the ammonium persulphate of 10g, the ferric sulfate of 1g dissolve in 500ml water, stir 18 hours.
Remove residual ion in the solution with spent ion exchange resin after the ammonia treatment, through polystyrolsulfon acid ammonia-poly-(3,4-ethylene dioxy base) the thiophene aqueous solution that obtains mazarine 1.6wt% after the dispersion treatment.
The polystyrolsulfon acid of the 1.6wt% of the 10g that obtains-poly-(3,4-ethylene dioxy base) the thiophene aqueous solution, 0.15g 2-[4-(2-hydroxyethyl) phenoxy group] the N-N-methyl-2-2-pyrrolidone N-of ethanol (HQEE) and 0.3g mixes and stirs, and obtains the mazarine solid electrolyte solution.
(making of solid electrolytic capacitor)
After being impregnated in the winding capacitance work in-process sub-prime with the vacuum decompression method, carry out drying at 120 ℃ of degree in the baking ovens to solid electrolyte solution, the dipping that uses the same method then/drying 2 times obtains containing the sub-prime of solid electrolyte.After the sub-prime that will contain the solid solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor.(capacity, ESR), its result is as shown in table 2 for the performance of evaluation solid electrolytic capacitor.
Embodiment 10
The polystyrolsulfon acid of the 1.6wt% of the 10g that embodiment 9 obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution, the 4-nitrophenols of 0.15g mixes stirring, obtains the mazarine solid electrolyte solution.
After being impregnated into solid electrolyte solution in the winding capacitance work in-process sub-prime with the vacuum decompression method, in 120 ℃ of degree baking ovens, carry out drying, after flooding the ammonium adipate aqueous solution of 10wt% then, in 120 ℃ of degree baking ovens, carry out drying, after the sub-prime that will contain the solid solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor.Method evaluation similarly to Example 9, its result is as shown in table 2.
Embodiment 11
The polystyrolsulfon acid of the 1.6wt% of the 10g that embodiment 9 obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution, the vanillyl alcohol of 0.3g mixes stirring, obtains the mazarine solid electrolyte solution.
Similarly to Example 9, obtain solid electrolytic capacitor respectively, evaluation result is as shown in table 2.
Embodiment 12
The polystyrolsulfon acid of the 1.6wt% of the 10g that embodiment 9 obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution, 3,4 of 0.2g, the 5-tri-methoxybenzoate, the triethylene glycol of 0.3g mixes stirring, obtains the mazarine solid electrolyte solution.
Similarly to Example 9, obtain solid electrolytic capacitor respectively, evaluation result is as shown in table 2.
Embodiment 13
The polystyrolsulfon acid of the 1.6wt% of the 10g that embodiment 9 obtains-poly-(3,4-ethylene dioxy base) the thiophene aqueous solution, the 4-amino-phenol of 0.1g, the 2-[4-of 0.15g (2-hydroxyethyl) phenoxy group] ethanol, 0.15g triethylene glycol mix to stir, obtain the mazarine solid electrolyte solution.
Similarly to Example 9, obtain solid electrolytic capacitor respectively, evaluation result is as shown in table 2.
Embodiment 14
On the anode foils of the condition that changes into of 105 ℃ of 9V, behind the solid electrolyte solution of dipping embodiment 9, in 120 ℃ of degree baking ovens, carry out drying, obtain containing the sub-prime of solid electrolyte.Make carbon film and silverskin then as negative electrode.
Behind the envelope film, obtain solid electrolytic capacitor.(capacity, ESR), its result is as shown in table 2 for the performance of evaluation solid electrolytic capacitor.
(comparative example 2)
Have only the same method evaluation with polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.6wt% of the 10g of embodiment 9 preparation and embodiment 9, its result is as shown in table 2.
Table 2
Figure A200810049110D00161
With shown in the table 1, the electroconductibility that aromatics adds conductive polymer composition among the embodiment 1 to embodiment 7 does not improve more than 100 times than not adding conductive polymer composition, and the electroconductibility of embodiment 8 is higher more than 10 times than not adding conductive polymer composition.Also have and do not add conductive polymer composition and compare aromatics and add conductive polymer composition higher thermotolerance is all arranged.
As shown in table 2, do not add conductive polymer composition and compare and use aromatics to add conductive polymer composition to have heavy body and low ESR, and under hot environment, can keep the performance of solid electrolytic capacitor yet as electrolytical solid electrolytic capacitor.

Claims (9)

1. conductive polymer composition, it is characterized in that comprising at least electroconductive polymer and polyanion, and aromatics, this electroconductive polymer is meant polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyaniline and derivative thereof, metaldehyde class and derivative thereof, poly-vinylene thiophene-based and derivative thereof, at least a in the multipolymer of polyethylene click and derivative thereof and these compounds; This polyanion contains carboxyl, at least a functional group in the sulfonic group; This aromatics contains-oxyl, nitro, at least a functional group in the amino.
2. conductive polymer composition according to claim 1, wherein said aromatics also contains carboxyl, hydroxyl, cyano group, sulfonic group, carbonyl, amide group, ester group, at least a functional group in fluorine-based.
3. according to claim 1,2 described a kind of conductive polymer compositions also contain doping agent, and electroconductibility is adjusted wedding agent, resinous principle, at least a in the conductive particle.
4. according to a kind of conductive polymer composition described in the claim 1～3, wherein contain ionic conductivity compound or ionic compound.
5. solid electrolyte is characterized in that containing a kind of conductive polymer composition described in the claim 1～4.
6. solid electrolytic capacitor, it is characterized in that having the anode bodies of making by metal porous body at least, be formed at the medium layer on the described metallic surface, the solid electrolyte layer between this medium layer and the cathode, and cathode, in the described solid electrolyte layer, have at least one deck to comprise electroconductive polymer and polyanion, and aromatics, this aromatics contains-oxyl, nitro, at least a functional group in the amino.
7. solid electrolytic capacitor according to claim 6, wherein said aromatics also contains carboxyl, hydroxyl, cyano group, sulfonic group, carbonyl, amide group, ester group, a kind of functional group in fluorine-based.
8. according to claim 6,7 described a kind of solid electrolytic capacitors, the polyanion in the wherein said solid electrolyte layer are poly-sulfonic acid class or salt, and polycarboxylic acid or salt.
9. according to a kind of solid electrolytic capacitor described in the claim 6～8, in the wherein said solid electrolyte layer, contain doping agent, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, the ionic conductivity compound, at least a in the ionic compound.
CN2008100491101A 2008-01-18 2008-01-18 Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer Expired - Fee Related CN101486839B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100491101A CN101486839B (en) 2008-01-18 2008-01-18 Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100491101A CN101486839B (en) 2008-01-18 2008-01-18 Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer

Publications (2)

Publication Number Publication Date
CN101486839A true CN101486839A (en) 2009-07-22
CN101486839B CN101486839B (en) 2011-08-17

Family

ID=40889909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100491101A Expired - Fee Related CN101486839B (en) 2008-01-18 2008-01-18 Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer

Country Status (1)

Country Link
CN (1) CN101486839B (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136305A1 (en) * 2011-04-08 2012-10-11 Heraeus Precious Metals Gmbh & Co. Kg Process for improving the electrical parameters in capacitors comprising pedot/pss as solid electrolyte, by means of additives
CN104177566A (en) * 2014-08-26 2014-12-03 太仓碧奇新材料研发有限公司 Polypyrrole conductive composite material for 3D printing and preparation method of polypyrrole conductive composite material for 3D printing
CN104193921A (en) * 2014-08-26 2014-12-10 太仓碧奇新材料研发有限公司 Poly(ethylenedioxy thiophene) conducting composite material for 3D printing and preparation method thereof
CN104204086A (en) * 2012-03-12 2014-12-10 赫劳斯贵金属有限两和公司 Addition of polymers to thiophene monomers in the in situ polymerization
CN104672447A (en) * 2015-02-21 2015-06-03 桂林理工大学 Preparation method of polypyrrole with high specific capacitance
CN102956364B (en) * 2011-08-17 2015-10-28 海洋王照明科技股份有限公司 A kind of double electric layer capacitor electrolytic solution and double electric layer capacitor
CN107430939A (en) * 2015-03-31 2017-12-01 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
CN107615424A (en) * 2015-05-29 2018-01-19 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
CN111091972A (en) * 2019-12-02 2020-05-01 湖南艾华集团股份有限公司 Manufacturing method of charge-discharge-resistant solid-state aluminum electrolytic capacitor
CN111247609A (en) * 2017-10-18 2020-06-05 凯米特电子公司 Conductive polymer dispersions for improved reliability
CN112979927A (en) * 2019-12-17 2021-06-18 深圳新宙邦科技股份有限公司 Composition, polymer for capacitor and capacitor
CN113025056A (en) * 2021-02-25 2021-06-25 浙江恒业成有机硅有限公司 Conductive silicone rubber and preparation method thereof
CN113228214A (en) * 2018-10-29 2021-08-06 宝力珠股份有限公司 High yield storage material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020059672A1 (en) * 2018-09-21 2020-03-26 日本ケミコン株式会社 Solid electrolytic capacitor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19841803A1 (en) * 1998-09-12 2000-03-16 Bayer Ag Organic electroluminescent device, i.e. light-emitting diode, has hole-injecting layer of polymeric organic conductor formed by coating from solution or from sub-micron dispersion
CN101040002B (en) * 2004-08-30 2011-08-17 信越聚合物株式会社 Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical information recording medium
JP4519679B2 (en) * 2005-02-21 2010-08-04 Ｎｅｃトーキン株式会社 Conductive polymer composition and solid electrolytic capacitor using the same

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136305A1 (en) * 2011-04-08 2012-10-11 Heraeus Precious Metals Gmbh & Co. Kg Process for improving the electrical parameters in capacitors comprising pedot/pss as solid electrolyte, by means of additives
CN102956364B (en) * 2011-08-17 2015-10-28 海洋王照明科技股份有限公司 A kind of double electric layer capacitor electrolytic solution and double electric layer capacitor
CN104204086A (en) * 2012-03-12 2014-12-10 赫劳斯贵金属有限两和公司 Addition of polymers to thiophene monomers in the in situ polymerization
CN104204086B (en) * 2012-03-12 2016-11-02 赫劳斯贵金属有限两和公司 Polymerization is added in thiophene monomer polymer in position
CN104177566A (en) * 2014-08-26 2014-12-03 太仓碧奇新材料研发有限公司 Polypyrrole conductive composite material for 3D printing and preparation method of polypyrrole conductive composite material for 3D printing
CN104193921A (en) * 2014-08-26 2014-12-10 太仓碧奇新材料研发有限公司 Poly(ethylenedioxy thiophene) conducting composite material for 3D printing and preparation method thereof
CN104672447A (en) * 2015-02-21 2015-06-03 桂林理工大学 Preparation method of polypyrrole with high specific capacitance
CN104672447B (en) * 2015-02-21 2017-01-04 桂林理工大学 A kind of preparation method of high specific capacitance polypyrrole
CN107430939B (en) * 2015-03-31 2019-06-28 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
US10685787B2 (en) * 2015-03-31 2020-06-16 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor including conductive polymer with copolymer dopant and conductive polymer dispersion
CN107430939A (en) * 2015-03-31 2017-12-01 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
CN107615424B (en) * 2015-05-29 2019-09-27 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
CN107615424A (en) * 2015-05-29 2018-01-19 松下知识产权经营株式会社 Electrolytic capacitor and electroconductive polymer dispersion
US10388463B2 (en) 2015-05-29 2019-08-20 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor and conductive polymer dispersion
CN111247609A (en) * 2017-10-18 2020-06-05 凯米特电子公司 Conductive polymer dispersions for improved reliability
CN111247609B (en) * 2017-10-18 2022-09-27 凯米特电子公司 Conductive polymer dispersions for improved reliability
CN113228214A (en) * 2018-10-29 2021-08-06 宝力珠股份有限公司 High yield storage material
US11955280B2 (en) 2018-10-29 2024-04-09 PolyJoule, Inc. High yield storage materials
CN111091972A (en) * 2019-12-02 2020-05-01 湖南艾华集团股份有限公司 Manufacturing method of charge-discharge-resistant solid-state aluminum electrolytic capacitor
CN111091972B (en) * 2019-12-02 2022-03-01 湖南艾华集团股份有限公司 Manufacturing method of charge-discharge-resistant solid-state aluminum electrolytic capacitor
CN112979927A (en) * 2019-12-17 2021-06-18 深圳新宙邦科技股份有限公司 Composition, polymer for capacitor and capacitor
CN112979927B (en) * 2019-12-17 2021-12-14 深圳新宙邦科技股份有限公司 Composition, polymer for capacitor and capacitor
CN113025056A (en) * 2021-02-25 2021-06-25 浙江恒业成有机硅有限公司 Conductive silicone rubber and preparation method thereof

Also Published As

Publication number Publication date
CN101486839B (en) 2011-08-17

Similar Documents

Publication Publication Date Title
CN101486839B (en) Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer
CN101302341B (en) Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode
CN101302339B (en) Conductive polymer composition and solid electrolyte capacitor using the same
CN101486836A (en) Conductive macromolecular solution, preparation thereof, conductive polymer coated film and solid electrolyte capacitor
CN101302340A (en) Conductive composite body, conductive polymer composition and electronic component using the conductive polymer composition
JP4077675B2 (en) Aqueous dispersion of complex of poly (3,4-dialkoxythiophene) and polyanion and method for producing the same
Sathiyanarayanan et al. Soluble conducting poly ethoxy aniline as an inhibitor for iron in HCl
EP1730212B1 (en) Organic formulations of polythiophenes and polypyrrole polymers made with polymeric acid colloids for electronics applications
EP1615971B2 (en) Water dispersible polythiophenes made with polymeric acid colloids
JP4688125B2 (en) Conductive polymer and solid electrolytic capacitor using the same
CN101486837A (en) Conductive macromolecular solution, conductive polymer coated film and solid electrolyte
JP2000336154A (en) Production of electroconductive polymer
JP4418198B2 (en) Solid electrolytic capacitor and manufacturing method thereof
CN101488398A (en) Solid electrolyte, electrolytic capacitor using the solid electrolyte and production method for the solid electrolyte capacitor
CN101486849B (en) Conductive paint, conductive composition and electronic component using the same
CN101486838A (en) Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer
JP4573363B1 (en) Process for producing organic solvent-based conductive polymer dispersion and its application
CN101303937B (en) Solid electrolytic capacitor and method for preparing the same
CN101303910B (en) Conductivity composite material and capacitor
JP2011138814A (en) Electrolytic capacitor and method of manufacturing the same
WO2010110200A1 (en) Electroconductive coating composition and process for production of electroconductive coating film
JP2011157535A (en) Method of production of electroconductive composition
JP3464733B2 (en) Solid electrolytic capacitor and method of manufacturing the same
CN101486841A (en) Conductive macromolecular solution, preparation thereof, conductive polymer coated film and solid electrolyte
CN101303938B (en) Solid electrolytic capacitor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110817