CN101486837A - Conductive macromolecular solution, conductive polymer coated film and solid electrolyte - Google Patents
Conductive macromolecular solution, conductive polymer coated film and solid electrolyte Download PDFInfo
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- CN101486837A CN101486837A CNA200810049107XA CN200810049107A CN101486837A CN 101486837 A CN101486837 A CN 101486837A CN A200810049107X A CNA200810049107X A CN A200810049107XA CN 200810049107 A CN200810049107 A CN 200810049107A CN 101486837 A CN101486837 A CN 101486837A
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Abstract
An electroconductive polymer solution is formed by the chemical oxidation polymerization of monomers containing electroconductive high molecules, and a mixed solution containing sulfonic group high molecules, inorganic acid, an organic acid compound, a solvent, an oxidant and a catalyst. Electroconductive high molecules with high conductivity can be obtained. The coating film of the electroconductive polymer solution has high conductivity and transmission and low resistance. When the electroconductive polymer coating film is applied to a solid electrolyte in a solid electrolytic capacitor, low ESR and other excellent properties can be achieved.
Description
Technical field
The present invention relates to conductive-polymer solution, conductive polymer coated film, and the solid electrolyte that uses this conductive-polymer solution.
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.
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 the multipolymer of these materials etc.These electroconductive polymers can be by chemical oxidative polymerization and the preparation of electrolytic polymerization method.
But the electrolytic polymerization method is the solid electrolyte mixing solutions of forming with the monomer of electroconductive polymer and doping agent, adds ready-made electrode materials, forms the film of electroconductibility high score 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, just 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, the solvability of organic solvent will reduce.Therefore, what obtain mostly is insoluble solid shape powder, is difficult to use with this state.
For overcoming the above problems, 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.
Electroconductive polymer layer as the solid electrolyte of solid electrolytic capacitor etc. uses pyroles, thiophene-based, and phenyl aminess etc. are as monomer.When forming the electroconductive polymer of described solid electrolyte, the main chemical oxidative polymerization method that uses, this method forms the electroconductive polymer layer by add oxygenant and doping agent in electroconductive polymer thereby induce 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.Therefore, if only form the solid electrolyte of solid electrolytic capacitor with the soluble conductive macromolecular solution, then the ESR of solid electrolytic capacitor and electrostatic capacity have both and select one relation, and therefore the example that uses seldom.
Summary of the invention
The present invention provides a kind of conductive-polymer solution and conductive polymer coated film for solving the high resistance of electroconductive polymer, and this films is to have the resistivity of reducing, and increases transmittance.And the ESR performance issue of the solid electrolytic capacitor of electroconductive polymer is used in solution.A kind of solid electrolyte of high conduction is provided.
Conductive-polymer solution of the present invention contains the sulfonic group polymer by the monomer that contains electroconductive polymer, mineral acid, and organic acid compound, the mixing solutions of solvent and oxygenant or catalyzer forms through chemical oxidative polymerization.Wherein said organic acid compound contains more than one sulfonic group at least.Have at least a program to adopt the emulsification program in the preparation procedure of conductive-polymer solution.Oxygen content is preferably below 8 ppm by weight during chemical oxidising polymerisation.
Also contain doping agent in the conductive-polymer solution of the present invention, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound etc.
Conductive polymer coated film of the present invention and solid electrolyte solvent in removing conductive-polymer solution obtains.
Conductive-polymer solution conductive polymer coated film of the present invention has high conductivity and high transmission rate.Use the solid electrolytic capacitor of the solid electrolyte for preparing among the present invention to have low ESR.
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 solution of the present invention by the monomer that contains electroconductive polymer, contain the sulfonic group polymer, mineral acid, organic acid compound, the mixing solutions of solvent and oxygenant or catalyzer forms through chemical oxidative polymerization.Wherein said organic acid compound contains more than one sulfonic group at least.Have at least a program to adopt the emulsification program in the preparation procedure of conductive-polymer solution.Also contain doping agent in the conductive-polymer solution, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound etc.
(monomer of electroconductive polymer)
As long as the monomer as electroconductive polymer of the present invention can aggregate into electroconductive polymer, there is not particular restriction.For example: pyroles and derivative thereof, thiophene-based and derivative thereof, acetylene class and derivative thereof, inferior benzene class and derivative thereof, phenylene 1, inferior vinyl of 2-and derivative thereof, phenyl amines and derivative thereof, acetaldehyde class and derivative thereof, vinylene thiophene-based and derivative thereof etc.Especially from chemical stabilization under air atmosphere, the good aspect of operability is considered, preferably uses pyroles and derivative thereof, thiophene-based and derivative thereof, phenylene 1, inferior vinyl of 2-and derivative thereof, phenyl amines and derivative thereof etc.
Monomer object lesson as preferred use electroconductive polymer can be enumerated: pyrroles, 3-methylpyrrole, 3-carboxy pyrrole, 3-methyl-4-propyloic pyrroles, 3-methoxyl group pyrroles, 3-hexyloxy pyrroles, 3-methyl-4-hexyloxy pyrroles's etc. pyroles; Thiophene, 3 methyl thiophene, 3-hexyl thiophene, 3-hydroxyl thiophene, the 3-methoxythiophene, 3-hexyloxy thiophene, 3-octyloxy thiophene, 3,4-dihydroxyl thiophene, 3, the 4-dimethoxy-thiophene, 3,4-diethoxy thiophene, 3,4-two hexyloxy thiophene, 3,4-oxygen base in two heptan thiophene, 3,4-two octyloxy thiophene, 3,4-didecyl oxygen base thiophene, 3, the 4-Ethylenedioxy Thiophene, 3, the inferior third dioxy base thiophene of 4-, 3,4-butylene dihydroxyl thiophene, 3-methyl-4-methoxythiophene, 3, the 4-ethene dioxythiophene, 3, the thiophene-based of 4-butylene dioxy thiophene etc.; And aniline, 2-aminotoluene, 3-isobutyl-aniline, 2-aniline sulfonic acid, the phenyl amines of 3-aniline sulfonic acid etc. etc.
The monomer of electroconductive polymer can aggregate into electroconductive polymer by chemical oxidative polymerization.Under the condition that has oxygenant or catalyzer, be oxidized to electroconductive polymer from the monomer chemistry of electroconductive polymer.As long as having more than 2, the polymeric unit of electroconductive polymer can obtain good electrical conductivity.
Can use ammonium persulphate as oxygenant, Sodium Persulfate, the persulphate of Potassium Persulphate etc., iron(ic) chloride (III), ferric sulfate (III), cupric chloride (II), the transistion metal compound of tosic acid iron (III) etc., silver suboxide, the metal oxide of Cs2O (Se) etc., hydrogen peroxide, superoxide such as ozone, the organo-peroxide of peroxidation benzene first phthalein etc. 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 ℃.
(containing the sulfonic group polymer)
Electroconductive polymer monomer of the present invention can and contain sulfonic group at oxygenant or catalyzer and carry out chemical oxidising polymerisation in the presence of high molecular.Contain sulfonic group high molecular in the presence of the polymeric electroconductive polymer can obtain good solubility and electroconductibility.
As containing sulfonic group polymer (polyanion) so long as side chain has sulfonic polymer 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.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 persulphates such as ammonium persulphate, Sodium Persulfate, Potassium Persulphate 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.
Containing the high molecular object lesson of sulfonic group can enumerate: 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 that contains the sulfonic group polysalt 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.
Contain the high molecular molecular-weight average of sulfonic group 1,000～1,000,000 scope, preferred 5,000～800,000.
The mass ratio that contains sulfonic group polymer and electroconductive polymer (contains sulfonic polymer: 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 mass ratio 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.
(mineral acid, organic acid compound)
The monomer of electroconductive polymer of the present invention is at oxygenant or catalyzer, when carrying out chemical oxidising polymerisation under the existence of mineral acid and organic acid compound, and the electroconductibility of the electroconductive polymer that can be improved.Can enumerate as mineral acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoroboric acid, mineral acid such as hydrofluoric acid and salt thereof etc.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, 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, adjacent carboxyl Phenylsulfonic acid, sulfobenzoic acid, 3,5-disulfonic acid phenylformic acid, sulfophthalic acid, sulfo group pure terephthalic acid, cysteic acid, the 5-sulphosalicylic acid contains sulfonic polymer etc.Also can use these ammonium salt, metal-salt etc.As long as this have in inorganic acids and the organic sulfonic acid class each more than one, various acids can use separately also and can use simultaneously, at this without any restriction.
As mineral acid or organic acid compound content, respectively with the preferred 99:1～10:90 of monomeric mass ratio of electroconductive polymer.As long as in this scope, can obtain higher electroconductibility, but when mineral acid or organic acid compound are lower than this scope, the inadequate tendency of electroconductibility is arranged then.
(emulsification)
When the monomer of electroconductive polymer of the present invention carries out chemical oxidising polymerisation, under the state of monomer that contains electroconductive polymer and solvent, can improve the electroconductibility of electroconductive polymer through emulsification.Preferably carry out emulsification in the presence of high molecular containing sulfonic group, more preferably containing the sulfonic group polymer, mineral acid carries out emulsification under the existence of organic acid compound.Can improve the monomer and the touch opportunity that contains the sulfonic group compound of electroconductive polymer when under containing the monomeric state of sulfonic group polymer and electroconductive polymer, passing through emulsification, contain the doping efficiency of sulfonic group compound toward electroconductive polymer with raising.When under the state of the monomer that contains electroconductive polymer and oxygenant or catalyzer, passing through emulsification, can improve the touch opportunity of monomer and the oxygenant or the catalyzer of electroconductive polymer, contain the chemical oxidising polymerisation efficient of sulfonic group compound toward electroconductive polymer with raising.
As long as can will contain the monomer of electroconductive polymer as emulsifying manner of the present invention, solvent and mixing solutions produce emulsion and get final product.Can use known method arbitrarily, this to its concrete emulsifying manner without any restriction.For example can enumerate: high-pressure emulsification, decompression emulsification, (dispersion) emulsification that runs up, ultrasonic emulsification, emulsification pretreatment etc., as long as can obtaining good effect more than 1MPa, emulsification pressure is preferably more than the 10MPa as high-pressure emulsification.Can use the ultrasonic wave of 20～400kHz scope as ultrasonic emulsification.
When the polymerization electroconductive polymer, the state that the oxygen content in its mixing solutions is few can reduce the bad influence of oxygen down, to improve the electroconductibility of electroconductive polymer.Under the temperature of 25 degree, the oxygen content in the mixing solutions is below 8 ppm by weight.Be preferably below 6 ppm by weight, more preferably below 3 ppm by weight.
Oxygen content in the mixing solutions 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 mixing solutions reduces its oxygen content.The preferred pressure below 0.05MPa.The irradiation ultrasonic wave can reduce more oxygen in the solution when reduced pressure treatment, 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, causes reducing the capillary compound of leading solution so long as can improve the surfactivity of solution and gets final product.For example can use defoamer, cats product, anion surfactant, nonionic surface active agent, zwitterionics, alcohol compound etc.
(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.
For electroconductibility or the film-forming properties that improves above-mentioned electroconductive polymer can add doping agent arbitrarily in above-mentioned conductive-polymer solution, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, ionic compound etc.
(doping agent, electroconductibility is adjusted agent)
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 the content of doping agent 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 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 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 can add ionic conductivity compound and ionic compound.Add the ion transmission energy that ionic conductivity compound and ionic compound can improve conductive polymer coated film and solid electrolyte.
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.Its boiling point was preferably more than 150 degree when ionic compound was ionic liquid.Solid ion compound more preferably.
Can example enumerate as negatively charged ion: carboxylic compound, the organic anion of sulfonic group compound etc., sulfuric acid, the no organic anion of hydrochloric acid etc., iodine, the halide anion of bromine etc. etc.Can example enumerate as positively charged ion: 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.From the preferred cationic nitrogenous of cationic electric stability.
(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 known coating method, print process, pickling process, spraying method etc.At this without any restriction.
Another object of the present invention is by using above-mentioned conductive-polymer solution and film, a kind of solid electrolyte with high conductivity is provided, using the solid electrolytic capacitor of solid electrolyte to have excellent ESR property.
(solid electrolytic capacitor)
Example to solid electrolytic capacitor of the present invention describes below.
Solid electrolytic capacitor of the present invention can: 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 or above-mentioned conductive polymer coated film through removing to desolvate in this solid electrolyte layer by above-mentioned conductive-polymer solution.
(anode bodies)
At this, 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 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) 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, possesses electrolytic paper is arranged.Electrolytic paper is located between 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
Conductive-polymer solution of the present invention contains the sulfonic group polymer by containing the monomer of electroconductive polymer, mineral acid, organic acid compound, the mixing solutions of solvent and forming.Obtain the electroconductive polymer of high electrical conductivity.Use filming of this conductive-polymer solution to have high printing opacity and low-resistance performance.Use the solid electrolyte of this conductive-polymer solution to have low resistance, can obtain the solid electrolytic capacitor performance of the excellence of low ESR etc.
(embodiment)
To conductive-polymer solution of the present invention, the object lesson of conductive polymer coated film and solid electrolytic capacitor describes below.The present invention is not only limited to following example.
Embodiment 1
With 3 of 5g, 4-ethylene dioxythiophene (EDOT), the polystyrolsulfon acid aqueous solution of the 10wt% of 150g (weight average molecular weight 120,000), the adjacent carboxyl Phenylsulfonic acid of 10g, the vitriol oil of 10g, the deionized water of the ferric sulfate of 1g (III) and 500g mixes, and obtains mixing solutions.
Mixing solutions is put into the reaction vessel of 1000ml, after reaction vessel seals the oxygen of reaction vessel interior is replaced nitrogen.Then, add the ammonium persulphate of 10g in the emulsion, stirred 18 hours.
Spent ion exchange resin obtains electroconductive polymer (polystyrolsulfon acid-poly-(3, the 4-ethylene dioxy base) thiophene) aqueous solution 1 of mazarine 1.6wt% by the residual ion in the filtering solution.
With the electroconductive polymer aqueous solution of the 1.6wt% of the 5g that obtains, the dimethyl sulfoxide (DMSO) of 0.25g (DMSO), the ethanol of 5g mix stir after, with this mixing solutions be applied on glass after, in 120 ℃ of degree baking ovens, carry out drying, the conductive polymer coated film that obtains.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Embodiment 2
With 3 of 5g, 4-ethylene dioxythiophene (EDOT), the polystyrolsulfon acid aqueous solution of the 10wt% of 150g (weight average molecular weight 120,000), the adjacent carboxyl Phenylsulfonic acid of 10g, the vitriol oil of 10g, the deionized water of the ferric sulfate of 1g (III) and 500g mixes, and obtains mixing solutions.Mixing solutions is carried out high-pressure emulsification under the pressure of 50MPa.
The emulsion that high-pressure emulsification is crossed is put into the reaction vessel of 1000ml, after reaction vessel seals the oxygen of reaction vessel interior is replaced nitrogen.Then, add the ammonium persulphate of 10g in the emulsion, stirred 18 hours.
The residual ion in the solution is removed in spent ion exchange resin and ultra-filtration, obtains electroconductive polymer (polystyrolsulfon acid-poly-(3, the 4-ethylene dioxy base) thiophene) aqueous solution 2 of mazarine 1.6wt%.
The electroconductive polymer aqueous solution of the 1.6wt% of the 5g that obtains, the dimethyl sulfoxide (DMSO) of 0.25g (DMSO), the ethanol of 5g mix stir after, with this mixing solutions be applied on glass after, in 120 ℃ of degree baking ovens, carry out drying, the conductive polymer coated film that obtains.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Embodiment 3
Except that the adjacent carboxyl Phenylsulfonic acid with the 10g of embodiment 2 changes the Phenylsulfonic acid of 5g into, with obtain the electroconductive polymer aqueous solution 3 and conductive polymer coated film with the same method of embodiment 2 and estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Comparative example 1
In the reaction vessel of 1000ml, 3 of difference weighing 5g, 4-ethylene dioxythiophene, the polystyrolsulfon acid aqueous solution of the 10wt% of 150g (weight average molecular weight 120,000), the deionized water of the ferric sulfate of 1g (III) and 500g, the ammonium persulphate of 10g obtains mixing solutions.This mixing solutions was stirred 18 hours.
The residual ion in the solution is removed in spent ion exchange resin and ultra-filtration, obtains electroconductive polymer (polystyrolsulfon acid-poly-(3, the 4-ethylene dioxy base) thiophene) aqueous solution 4 of mazarine 1.6wt%.
The electroconductive polymer aqueous solution of the 1.6wt% of the 5g that obtains, the dimethyl sulfoxide (DMSO) of 0.25g (DMSO), the ethanol of 5g mix stir after, with this mixing solutions be applied on glass after, in 120 ℃ of degree baking ovens, carry out drying, the conductive polymer coated film that obtains.Estimate the specific conductivity and the transparence of conductive polymer coated film, its result is as shown in table 1.
Table 1
| Specific conductivity (S/cm) | Transparence (%) | Surface resistivity (Ω/sq) | |
| Embodiment 1 | 598 | 88.2 | 230 |
| Embodiment 2 | 735 | 88.3 | 160 |
| Embodiment 3 | 684 | 87.9 | 194 |
| Comparative example 1 | 115 | 83.5 | 1100 |
(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 winding capacitance work in-process sub-prime of guide pin on solid electrolytic paper and the fourth.
(preparation of solid electrolyte solution)
Respectively toward the electroconductive polymer aqueous solution 1 of 100g, the electroconductive polymer aqueous solution 2, the electroconductive polymer aqueous solution 3 in the electroconductive polymer aqueous solution 4, adds the triethylene glycol of 5g, the dimethyl sulfoxide (DMSO) of 5g (DMSO), the imidazoles of 1g obtains electroconductive polymer electrolyte solution 1 respectively, electroconductive polymer electrolyte solution 2 after mixing stirring, electroconductive polymer electrolyte solution 3, electroconductive polymer electrolyte solution 4.
Embodiment 4
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 electroconductive polymer electrolyte solution 1, 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 solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor.Estimate the ESR performance of solid electrolytic capacitor, its result is as shown in table 2.
Embodiment 5,6
With using electroconductive polymer electrolyte solution 2 (embodiment 5) respectively with embodiment 4 same methods, electroconductive polymer electrolyte solution 3 (embodiment 6) preparation solid electrolytic capacitor.Its result is as shown in table 2.
(comparative example 2)
With preparing solid electrolytic capacitors with electroconductive polymer electrolyte solution 4 respectively with embodiment 4 same methods.Estimate the ESR performance of solid electrolytic capacitor, its result is as shown in table 2.
Table 2
| Capacity (μ F) 120Hz | ESR(mΩ)100kHz | |
| Embodiment 4 | 445 | 11.3 |
| Embodiment 5 | 467 | 10.1 |
| Embodiment 6 | 466 | 10.7 |
| Comparative example 2 | 380 | 24.3 |
Shown in the embodiment in the table 11 to embodiment 3, containing filming of conductive-polymer solution that organic acid obtains with mineral acid during the electroconductive polymer polymerization compares electroconductibility with filming of the conductive-polymer solution that does not contain organic acid and mineral acid and improves nearly more than 5 times, transparence approximately improves more than 4～5%, and surface resistivity reduces more than 70%.Filming of this conductive-polymer solution has high-transmittance and low surface resistivity.
As shown in the embodiment 4 to embodiment 6 of table 2, more than the ESR reduction 13m Ω of the ESR that uses the solid electrolytic capacitor contain the solid electrolyte that organic acid and mineral acid obtain than the solid electrolytic capacitor that does not contain the solid electrolyte that organic acid and mineral acid obtain.Has good ESR performance.
Claims (9)
1. conductive-polymer solution is characterized in that containing the sulfonic group polymer by the monomer that contains electroconductive polymer, mineral acid, and organic acid compound, solvent, the mixing solutions of oxygenant and catalyzer forms through chemical oxidative polymerization.
2. conductive-polymer solution according to claim 1, wherein said organic acid compound contains more than one sulfonic group at least.
3. according to claim 1, a kind of conductive-polymer solution described in 2, wherein said to contain the sulfonic group polymer be polystyrolsulfon acid with and salt.
4. according to a kind of conductive-polymer solution described in the claim 1～3, wherein said electroconductive polymer is the polypyrrole class, polythiophene class, polyacetylene class, poly-inferior benzene class, polyphenylene 1, the inferior vinyl of 2-, polyaniline compound, the metaldehyde class, poly-vinylene thiophene-based, and at least a in these the multipolymer.
5. according to a kind of conductive-polymer solution described in the claim 1～4, have at least a program to adopt the emulsification program during chemical oxidising polymerisation.
6. according to a kind of conductive-polymer solution described in the claim 1～5, under the temperature of 25 degree, the oxygen content in its mixing solutions is below 8 ppm by weight.
7. by the conductive-polymer solution described in the claim 1～6, wherein also contain doping agent, electroconductibility is adjusted wedding agent, resinous principle, conductive particle, ionic conductivity compound, at least a in the ionic compound.
8. 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 1～7.
9. solid electrolyte is characterized in that being obtained through removing to desolvate by a kind of conductive-polymer solution described in the claim 1～7.
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| CN104078239A (en) * | 2014-06-25 | 2014-10-01 | 福建国光电子科技股份有限公司 | Polymerization solution for solid electrolytic capacitor to manufacture solid electrolyte layer |
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| CN102859612A (en) * | 2010-05-13 | 2013-01-02 | 日立化成工业株式会社 | Photosensitive Conductive Film, Method For Forming Conductive Membrane, And Method For Forming Conductive Pattern |
| CN104715923A (en) * | 2013-12-12 | 2015-06-17 | 三星电机株式会社 | Multilayer ceramic capacitor and manufacturing method thereof and mounting board therefor |
| CN104715923B (en) * | 2013-12-12 | 2018-05-29 | 三星电机株式会社 | Multilayer ceramic capacitor and its manufacturing method and installing plate |
| CN104078239A (en) * | 2014-06-25 | 2014-10-01 | 福建国光电子科技股份有限公司 | Polymerization solution for solid electrolytic capacitor to manufacture solid electrolyte layer |
| CN106067380A (en) * | 2016-06-06 | 2016-11-02 | 钰邦电子（无锡）有限公司 | Solid electrolytic capacitor packaging structure for improving electrical performance, capacitor unit and manufacturing method thereof |
| CN106397394A (en) * | 2016-08-30 | 2017-02-15 | 贝利化学（张家港）有限公司 | Method for preventing thiophene conducting polymeric monomer from discoloration |
| CN106397394B (en) * | 2016-08-30 | 2019-03-08 | 贝利化学（张家港）有限公司 | A method of prevent thiophene-based conductive polymerized monomer from changing colour |
| CN111431498A (en) * | 2020-03-31 | 2020-07-17 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer solution for crystal resonator and application thereof |
| CN111431498B (en) * | 2020-03-31 | 2023-09-01 | 中国科学院宁波材料技术与工程研究所 | Conductive polymer solution for crystal resonator and application thereof |
| CN114665149A (en) * | 2022-02-28 | 2022-06-24 | 合肥国轩高科动力能源有限公司 | Single-ion gel polymer electrolyte and application thereof |
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