CN101486836A - Conductive macromolecular solution, preparation thereof, conductive polymer coated film and solid electrolyte capacitor - Google Patents
Conductive macromolecular solution, preparation thereof, conductive polymer coated film and solid electrolyte capacitor Download PDFInfo
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- CN101486836A CN101486836A CNA2008100491065A CN200810049106A CN101486836A CN 101486836 A CN101486836 A CN 101486836A CN A2008100491065 A CNA2008100491065 A CN A2008100491065A CN 200810049106 A CN200810049106 A CN 200810049106A CN 101486836 A CN101486836 A CN 101486836A
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Abstract
An electroconductive polymer solution contains electroconductive high molecules and polyanion. Under 25 DEG C, the oxygen content in the electroconductive polymer solution is below 8 weight ppm. An electroconductive coating film using the solution has high transmittance and low resistance. Applied to a solid electrolytic capacitor, the electroconductive polymer solution can improve the conductivity of solid electrolysis and filling behavior, therefore, a solid electrolytic capacitor with low ESR and other excellent properties is obtained.
Description
Technical field
The present invention relates to conductive-polymer solution and preparation method thereof, and the solid electrolytic capacitor of conductive polymer coated film and this conductive polymer coated film of use (electrolytic capacitor).
Background technology
Conductive-polymer solution of the present invention and film and be expected to be applied to: conductive applications, electrically conducting coating, antistatic agent, electromagnetic shielding material, transparent electro-conductive material, battery material, capacitor material, 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, the thin typeization of indicating meter requires to reduce impedance and the high transparent electro-conductive material of employed electrical condenser at high-frequency region gradually.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, carbon-coating, and silver layer and the negative electrode that forms obtains as solid electrolyte.
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 described electrical condenser solid electrolyte, the main chemical oxidative polymerization method that uses, this method is by adding oxygenant and doping agent in electroconductive polymer, formation electroconductive polymer layer induces reaction on the oxide film of metal porous body.
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 the electroconductive polymer layer.In this technology, 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.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 to have begun the monomer of being 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.
So-called electroconductive polymer is the polypyrrole class normally, 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 solid electrolytic polymerization.
The electrolytic polymerization method is the monomer of electroconductive polymer and the solid electrolyte mixing solutions that doping agent is formed, and adds preformed electrode materials, forms electroconductive polymer and form film 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 solution with polyanionic compound.As the high molecular example of soluble conductive, the Baytron-P of H.C.Starck-VTECHLtd. production etc. is arranged on market.Yet it is lower that this electroconductive polymer has a high resistance system film.
Summary of the invention
The present invention is high resistance that solves electroconductive polymer and the problem of making film.And the problems such as performance of the solid electrolytic capacitor of electroconductive polymer are used in solution.
The present invention provides a kind of conductive polymer coated film and forms the conductive-polymer solution that this is filmed, and this films is to have the resistivity of reducing, and increases transmittance.
Conductive-polymer solution of the present invention contains electroconductive polymer and polyanion and solvent, and under the temperature of 25 degree, the oxygen content in this solution is below 8 ppm by weight.
In the conductive-polymer solution of the present invention, also contain tensio-active agent, doping agent, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound.
The present invention also provides a kind of preparation method of conductive-polymer solution, and this preparation method is that conductive-polymer solution is handled under the pressure below the 0.1MPa and obtained.Under reduced pressure can also obtain with ultrasonication.
Conductive polymer coated film of the present invention, above-mentioned conductive-polymer solution obtains through removing to desolvate.This conductive polymer coated film conductance is more than the 100S/cm.
Another object of the present invention is by the applying conductive macromolecular coating, provides a kind of excellent electric capacity that has, the solid electrolytic capacitor of ESR performance.
One deck at least in the solid electrolyte layer of solid electrolytic capacitor of the present invention is by under the temperature of 25 degree, and the sour cellulose content in the solution is that the following conductive-polymer solution of 8 ppm by weight forms.
Conductive-polymer solution in the present invention has long-term stability.The conductive polymer coated film of conductive-polymer solution formation can obtain having high conductivity and high transmission rate thus.
Solid electrolytic capacitor of the present invention can obtain having excellent capacity, the solid electrolytic capacitor of ESR performance.
Embodiment
Below, use example of the present invention is described.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 solution of the present invention, under the temperature of 25 degree, the sour cellulose content in this solution is below 8 ppm by weight, by electroconductive polymer and polyanion, and solvent and forming.Can add tensio-active agent as required, doping agent has resinous principle, and 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 can enumerate: 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 chemical stabilization under air atmosphere, the good aspect of operability is considered, preferably uses the polypyrrole class, polythiophene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound.
Object lesson as the electroconductive polymer of preferred use can be enumerated: 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,, for example can enumerate: water, N-Methyl pyrrolidone (NMP) so long as the solvent of solubilized or dispersion oxygenant or oxypolymerization catalyzer gets final product, 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 carry out chemical oxidising polymerisation in the presence of oxygenant or catalyzer and polyanion.The polymeric electroconductive polymer can obtain good solubility and electroconductibility under the polyanion containing.
(polyanion)
As polyanion so long as side chain has the carboxylic acid group, sulfonic group, sulfate, the polymer of phosphate can use.Then requiring as main chain is that following material constitutes: 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.Can enumerate as concrete example: 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 as: 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, but when polyanion is lower than this scope, the inadequate tendency of solvent solubility are arranged then.When being higher than this scope, then can not obtain sufficient electroconductibility sometimes.
(solvent)
As solvent,, for example can enumerate: water, N-Methyl pyrrolidone (NMP) so long as the solvent of solubilized or agent of dispersed electro-conductive oxidation polymer and polyanion gets final product, 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.
Conductive-polymer solution of the present invention, under the temperature of 25 degree, the sour cellulose content in this solution is below 8 ppm by weight.Be preferably below 6 ppm by weight, more preferably below 3 ppm by weight.The acid cellulose content can obtain high transmission rate and make film preferably when being lower than 8 ppm by weight.When being used for solid capacitor, this conductive-polymer solution can obtain higher impregnation to obtain excellent solid capacitor performance.
Sour cellulose content in the conductive-polymer solution can be used the decompression method, centrifuging, and methods such as tensio-active agent additive process reduce.
As the decompression method, can be used under the following pressure of 0.1MPa, the method for handling conductive-polymer solution reduces its sour cellulose content.The preferred pressure below 0.05MPa.When the reduced pressure treatment conductive-polymer solution, it is plain that the irradiation ultrasonic wave can be able to reduce more acid in the conductive-polymer solution, can improve and reduce oxygen efficient.Can use the scope of 20~400kHz to ultrasonic frequency, this to illuminating method without any restriction.
As tensio-active agent, intramolecularly has the hydrophilic and oleophilic group, and the capillary compound that causes reducing conductive-polymer solution so long as can improve the surfactivity of conductive-polymer solution gets final product, without any restriction.Can use defoamer, cats product, anion surfactant, nonionic surface active agent, zwitterionics, alcohol compound etc.For example can enumerate: fluorocarbon surfactant, the two fat of macromolecule polyethylene glycol, polyethers, polyoxyethylene glycol (PEG), polyoxyethylene nonylphenol ether, diglycollic amide stearic acid monoglyceride, alkyl, polyether (PO-EO multipolymer), fatty alcohol-polyoxyethylene ether, sugar ester, polyoxyethylene-polyoxypropylene multipolymer, defoamer, polyether glycol, diethanolamine, organic carboxyl acid, linear alkylbenzene sulphonic acid (LAS), the organic sulfonic acid of polyoxyethylenated alcohol sodium sulfate (AES) etc., the sulfuric acid of AESA (AESA) etc., amide and salt thereof, the triethylene glycol butyl ether, triethylene glycol butyl ether, triethylene glycol butyl ether, the triethylene glycol monobutyl ether, triglycol butyl ether, the ethers of butoxy triethylene glycol ether etc., methyl alcohol, ethanol, propyl alcohol, butanols, arabitol, 3-amino-1,2-propylene glycol, N.F,USP MANNITOL, glycol, glycol ether, triethylene glycol, the alcohol of poly-glycol etc. etc.As the preferred 0.5~80wt% of the addition of tensio-active agent.As long as in this scope, then can obtain good dispersion effect.
(doping agent, electroconductibility is adjusted agent)
Can the mixing and doping agent in order to improve its electroconductibility of above-mentioned electroconductive polymer, electroconductibility is adjusted drug.Electroconductibility is adjusted the performance that drug is adjusted film-forming properties 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.Can enumerate phosphorus pentafluoride (PF as Lewis acid
5), arsenic pentafluoride (AsF
5), boron trifluoride (BF
3), boron trichloride (BCl
3) etc.Can enumerate as protonic acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoroboric acid, mineral acid and salt thereof such as hydrofluoric acid, organic carboxyl acid, organic acid and salt thereof such as organic sulfonic acid, organic cyanogen compound etc.
Content as doping agent is the mol ratio (doping agent: electroconductive polymer) preferred 0.1:1~1:0.1, more preferably 0.5:1~7:1 of electroconductive polymer.When mol ratio is lower than this scope, then can not obtain sufficient electroconductibility sometimes.When mol ratio is higher than this scope, then can not obtain sufficient electroconductibility sometimes.
Adjust drug as electroconductibility and can use 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 mass ratio 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.
(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.
(electroconductive particle)
Can add electroconductive particle arbitrarily in the conductive-polymer solution of the present invention, for example can enumerate: carbon particles, graphite particle as electroconductive particle, carbon fiber, carbon nanotube, soccerballene (fullerene), copper, nickel, silver, gold, tin, iron, metallicss such as aluminium, metal oxide 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, so preferred.Replaceable any functional group on this carbon material.For example can enumerate: 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 solution 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, coupling agent, conductive fillers etc. do not have particular restriction.
Conductive polymer coated film of the present invention can be applied to above-mentioned conductive-polymer solution on the base material back by forming except that desolvating.Film-forming method can utilize coating method, print process, pickling process, spraying method etc.
As long as have definite shape, there is not particular restriction as base material.For example can enumerate: metal, metal acidulants, molding, glass, quartz, polyethylene (PE), polypropylene (PP), polymethylmethacrylate, polyester, polycarbonate, polycarbonate, polyethylene ether ether ketone (PEEK), the polyester naphthalene, amorphous quality polyethylene alkene, fluoride resin, polyethersulfone, polymeric amide etc.Conductive polymer coated film can obtain the conduction gonosome of high printing opacity when being applied on the transmitting substrate.
The conductance of conductive polymer coated film is preferably more than 100S/cm, more preferably more than 200S/cm.
Another object of the present invention is by using above-mentioned conductive-polymer solution and film, a kind of solid electrolytic capacitor with excellent ESR property being provided.
(solid electrolytic capacitor)
Example to solid electrolytic capacitor of the present invention describes below.
It has solid electrolytic capacitor of the present invention: anode bodies that is made of metal and cathode, and be located at medium layer and solid electrolyte layer between anode bodies and the cathode.Have at least 1 layer to obtain through removing to desolvate in this solid electrolyte layer by above-mentioned conductive-polymer solution.
(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 capacitor anode, tantalum (Ta), niobium (Nb) etc.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 use aluminium foil is carried out after etching and processing increases its surface-area, 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) conductive-polymer solution, then solvent is removed, 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 above-mentioned conductive polymer coated film.
(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, nickel and these mixture etc.The preparation method can prepare with electrical conductor paper tinsel or coating, does not have particular restriction.
Beneficial effect
In the present invention, can improve the system film properties of electroconductive polymer with electroconductibility that improves electroconductive polymer and the transparence that improves conductive polymer coated film by the sour cellulose content that reduces in the conductive-polymer solution.Can obtain high printing opacity, low-resistance transparent conductive body.
This conductive-polymer solution is applied to electroconductibility and the high filling that solid electrolytic capacitor can improve solid electrolytic.Obtain the solid electrolytic capacitor of the excellent properties of a kind of low ESR of having etc.
(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 ammonium persulphate of the polystyrolsulfon acid aqueous solution of the 30wt% of 50g (molecular-weight average 120,000) 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, the dimethyl sulfoxide (DMSO) of 0.25g (DMSO), after the ethanol of 5g mixes stirring, with this mixing solutions 0.09MPa that reduces pressure, the ultrasonic wave of 5 minutes 28kHz of irradiation obtains conductive-polymer solution.
With conductive-polymer solution be applied on glass after, carry out drying, the conductive polymer coated film that obtains at 120 ℃ of degree in the baking ovens.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Embodiment 2
Polystyrolsulfon acid-poly-(3 with the 1.5wt% of the 5g of embodiment 1 preparation, 4-ethylene dioxy base) the thiophene aqueous solution, 0.1g dihydroxy-benzene, the ethanol of 3g, 0.25g dialkyl ether ethylene glycol vinegar mix to stir after, with this mixing solutions 1kPa that reduces pressure, the ultrasonic wave of 1 minute 40kHz of irradiation obtains conductive-polymer solution.
With conductive-polymer solution be applied on glass after, carry out drying, the conductive polymer coated film that obtains at 120 ℃ of degree in the baking ovens.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Embodiment 3
Except that not shining ultrasonic wave all with embodiment 2 same methods prepare conductive polymer coated film and and the same method evaluation of embodiment 2, its result is as shown in table 1.
Embodiment 4
Polystyrolsulfon acid-poly-(3 with the 1.5wt% of the 5g of embodiment 1 preparation, 4-ethylene dioxy base) the thiophene aqueous solution, 0.1g dihydroxy-benzene, the ethanol of 3g, 0.005g defoamer mix to stir after, with this mixing solutions 1kPa that reduces pressure, the ultrasonic wave of 1 minute 40kHz of irradiation obtains conductive-polymer solution.
With conductive-polymer solution be applied on glass after, carry out drying, the conductive polymer coated film that obtains at 120 ℃ of degree in the baking ovens.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Comparative example 1
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation, the dimethyl sulfoxide (DMSO) of 0.25g (DMSO), the ethanol of 5g mix stir after, obtain conductive-polymer solution.
With conductive-polymer solution be applied on glass after, carry out drying, the conductive polymer coated film that obtains at 120 ℃ of degree in the baking ovens.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Table 1
Acid cellulose content (ppm) | Specific conductivity (S/cm) | Transparence (%) | Surface resistivity (Ω/sq) | |
Embodiment 1 | 6 | 350 | 87.4 | 380 |
Embodiment 2 | 2 | 430 | 87.9 | 357 |
Embodiment 3 | 3 | 425 | 87.6 | 376 |
Embodiment 4 | 3 | 438 | 88.1 | 361 |
Comparative example 1 | 9 | 280 | 85.8 | 420 |
Embodiment 5
(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 ammonium persulphate of the polystyrolsulfon acid aqueous solution of the 30wt% of 50g (molecular-weight average 120,000) and 10g, the ferric sulfate of 1g (III) is dissolved in the 1000ml water, stirs 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 1.7wt% after the dispersion treatment.
The polystyrolsulfon acid of the 1.7wt% of the 100g that obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution, the dimethyl sulfoxide (DMSO) of 5g (DMSO), after mixing stirring, with this mixing solutions 1kPa that reduces pressure, the ultrasonic wave of 5 minutes 40kHz of irradiation obtains conductive-polymer 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 conductive-polymer solution, the dipping that uses the same method then/drying 1 time 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 6
The polystyrolsulfon acid of the 1.7wt% of the 100g that obtains with embodiment 5-poly-(3,4-ethylene dioxy base) the thiophene aqueous solution, the butanols of 5g, the triethylene glycol of 5g, after the vinylformic acid hydroxyl phthalein amine (HEAA) of 3g mixes stirring, with this mixing solutions 1kPa that reduces pressure, the ultrasonic wave of 3 minutes 28kHz of irradiation obtains conductive-polymer solution.
After being impregnated in the winding capacitance work in-process sub-prime with the vacuum decompression method, carry out drying in the baking ovens to solid electrolyte solution, the dipping that uses the same method then/drying 1 time at 120 ℃ of degree.After flooding the ammonium adipate aqueous solution of 10wt% then, carry out drying in the baking ovens, after the sub-prime that will contain the solid solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor at 120 ℃ of degree.Method evaluation similarly to Example 5, its result is as shown in table 2.
(comparative example 2)
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.7wt% of the 100g of embodiment 5 preparation, the dimethyl sulfoxide (DMSO) of 5g (DMSO) mix stir after, obtain conductive-polymer solution.The method evaluation same with embodiment 5, its result is as shown in table 2.
Embodiment 7
On the anode foils of the condition that changes into of 105 ℃ of 9V, behind the solid electrolyte solution of dipping embodiment 6, 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 3)
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.7wt% of the 100g of embodiment 5 preparation, the dimethyl sulfoxide (DMSO) of 5g (DMSO) mix stir after, obtain conductive-polymer solution.The method evaluation same with embodiment 7, its result is as shown in table 2.
Table 2
Acid cellulose content (ppm) | Capacity (μ F) 120Hz | ESR(mΩ)100kHz | |
Embodiment 5 | 3 | 423 | 13 |
Embodiment 6 | 2 | 468 | 9.5 |
Comparative example 2 | 8 | 329 | 24 |
Embodiment 7 | 2 | 320 | 5 |
Comparative example 3 | 8 | 192 | 21 |
With shown in the table 1, when the sour cellulose content in the conductive-polymer solution of embodiment 1 to embodiment 4 is lower than 9ppm, specific conductivity is compared with the conductive-polymer solution of sour cellulose content 9ppm and is improved 25%~56%, and transparence approximately improves 2%, surface resistivity low 10%~15%.This conductive polymer coated film has high-transmittance and low surface resistivity.
As shown in table 2, use the ESR that can improve the capacity of solid electrolytic capacitor when containing the low conductive-polymer solution of sour cellulose content and reduce solid electrolytic capacitor.
Claims (10)
1. conductive-polymer solution, it is characterized in that containing polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyaniline and derivative thereof, metaldehyde class and derivative thereof, poly-1,2-vinylidene thiophene-based and derivative thereof, at least a and polyanion of the electroconductive polymer in the multipolymer of polyethylene click and derivative thereof and these compounds, and solvent, under the temperature of 25 degree, the oxygen content in this solution is below 8 ppm by weight.
2. conductive-polymer solution according to claim 1 wherein contains tensio-active agent, and this tensio-active agent has an above hydrophilic group.
3. conductive-polymer solution according to claim 2, wherein said tensio-active agent hydroxyl, fluorine-based,-oxyl, at least a functional group in the ether.
4. conductive polymer coated film is characterized in that being obtained through removing to desolvate by a kind of conductive-polymer solution described in the claim 1~3, and its conductance is more than the 100S/cm.
5. a kind of conductive polymer coated film according to claim 4, its transmittance are more than 60%.
6. the preparation method of conductive-polymer solution, it is characterized in that containing 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 and polyanion of electroconductive polymer in the multipolymer of polyethylene click and derivative thereof and these compounds, and the conductive-polymer solution of solvent is handled under the pressure below the 0.1MPa and is obtained.
7. the preparation method of conductive-polymer solution according to claim 6, described conductive-polymer solution obtains by ultrasonication under the pressure below the 0.1MPa.
8. the preparation method of conductive-polymer solution according to claim 7, described ultrasonic frequency is 20~400kHz.
9. solid electrolytic capacitor is characterized in that having the anode bodies that is made of metal, medium layer at least, solid electrolyte layer, and cathode, in the described solid electrolyte layer, have at least 1 layer to obtain through removing to desolvate by a kind of conductive-polymer solution described in the claim 1~3.
10. solid electrolytic capacitor according to claim 9 in the wherein said solid electrolyte layer, contains doping agent, and electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, at least a in the ionic compound.
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