CN101488398A - Solid electrolyte, electrolytic capacitor using the solid electrolyte and production method for the solid electrolyte capacitor - Google Patents
Solid electrolyte, electrolytic capacitor using the solid electrolyte and production method for the solid electrolyte capacitor Download PDFInfo
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- CN101488398A CN101488398A CNA2008100491099A CN200810049109A CN101488398A CN 101488398 A CN101488398 A CN 101488398A CN A2008100491099 A CNA2008100491099 A CN A2008100491099A CN 200810049109 A CN200810049109 A CN 200810049109A CN 101488398 A CN101488398 A CN 101488398A
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Abstract
A solid electrolyte contains electric conductivity high molecular, polyanion, salt thereof, and ionic compound, the boiling point of which is more than 150 degrees. Therefore, the solid electrolyte has excellent electronic conductivity and ionic conductivity. At least one layer in the solid electrolyte layers of a solid electrolytic capacitor contains electric conductivity high molecular, polyanion, salt thereof, and ionic compound, the boiling point of which is more than 150 degrees. The solid electrolyte has excellent electric capacitive properties and high temperature stability.
Description
Technical field
The present invention relates to solid electrolyte, relate to the solid electrolytic capacitor that is used to use this solid electrolyte.A kind of preparation method of solid electrolytic capacitor is provided.
Background technology
Comprise that solid electrolyte is expected to be applied to: conductive applications, electrically-conducting paint, electromagnetic shielding material, battery material, capacitor material, solar cell etc.
In recent years, along with the digitlization of electronic instrument, require to reduce of the impedance of employed capacitor gradually at high-frequency region.For adapting to this requirement, used gradually and had for example by aluminium, tantalum (Ta), the anode that the metal porous body of niobium valve actions such as (Nb) constitutes, the dielectric oxide film that constitutes by the metal oxide film of described valve action, on this oxidation 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 capacitor solid electrolyte, the main chemical oxidative polymerization method that uses, this method is by adding oxidant and dopant in electroconductive polymer, formation electroconductive polymer layer induces reaction on the oxidation film of metal porous body.
On the other hand, also use following technology: on the oxidation film of metal porous body, do not carry out polymerization, but by preparing the soluble conductive Polymer Solution independently, flood this polymer solution and enter metal porous body, be dried to then and film, thereby on oxidation film, form the electroconductive polymer layer.In this technology, the high molecular molecular weight of soluble conductive enters porous body inside with it permeability 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 capacitor with the soluble conductive Polymer Solution, then the ESR of capacitor 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 Polymer Solution:
(1) although its permeability that enters porous body is low, the soluble conductive macromolecule that molecular weight is big is used to prepare and can forms the soluble conductive Polymer Solution with low-resistance electroconductive polymer layer, thereby is combined near the electroconductive polymer layer that forms big thickness the outermost surface of porous body with chemical oxidative polymerization method.
(2) although its resistance height, the soluble polymer that molecular weight is little is used to prepare even also can promote in porous body inside the soluble conductive Polymer Solution of electroconductive polymer layer formation, thereby combines the electroconductive polymer layer as the matrix in the electrolysis polymerization with the electrolysis polymerization method.
3,4-ethene dioxythiophene (below be called " EDOT ") is oneself monomer through beginning to be used widely, and the big characteristics of one can obtain the low resistance electroconductive polymer exactly, therefore, when " EDOT " is used for the soluble conductive macromolecule, 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 Polymer Solution can only form has several times to 100 times or the electroconductive 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 problem.
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 metacetaldehyde class gathers 1,2-ethenylidene thiophene-based, and these copolymer etc.These electroconductive polymers can be by chemical oxidative polymerization and the preparation of electrolysis polymerization method.
The electrolysis polymerization method is the monomer of electroconductive polymer and the electrolyte mixed solution that dopant is formed, and adds preformed electrode material, forms electroconductive polymer thin 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 oxidant and catalyst, 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 dissolubility 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 dissolubility of organic solvent 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 this electroconductive polymer has high resistance and resistance enlarges markedly under high-temperature problem.
Summary of the invention
The present invention mainly solves the performance of the solid electrolytic capacitor that uses electroconductive polymer, and solves the low inferior problem of performance under the hot environment.
The present invention provides a kind of solid electrolyte that can obtain and has electronic component with this solid electrolyte of use.Use the performance of this solid electrolyte solid electrolytic capacitor excellence, and under hot environment, also can keep this excellent performance.
Solid electrolyte of the present invention is by electroconductive polymer and polyanion or/and salt, and the ionic compound of boiling point more than 150 degree formed.The ionic compound solution of this solid electrolyte by containing ionic compound forms through removing a part or most solvent with after the electroconductive polymer film that contains electroconductive polymer and polyanion or/and salt contacts.
In the solid electrolyte of the present invention, can also contain dopant, conductivity is adjusted bond, resinous principle, conductive particle, ionic conductivity compound.
Another object of the present invention is by using above-mentioned solid electrolyte, a kind of solid electrolytic capacitor with excellent properties being provided.And under hot environment, also can keep the performance of solid electrolytic capacitor.
The present invention also provides a kind of solid electrolytic capacitor preparation method, it is characterized in that having at least the preparation procedure of solid electrolyte layer; The ionic compound solution that contains ionic compound with contain the program that the electroconductive polymer film contacts; Remove the program of a part or most solvent.
Embodiment
Preference of the present invention advances to be not limited to following each example.For example, the inscape of these examples and mode correspondence or appropriate combination mutually to each other.
Solid electrolyte of the present invention is by electroconductive polymer and polyanion, and boiling point 150 the degree more than ionic compound and form.The ionic compound solution of this solid electrolyte by containing this ionic compound with contain electroconductive polymer and polyanion with and after the electroconductive polymer film of salt contacts, form through removing a part or most solvent.Can add dopant as required, resinous principle is arranged, conductivity is adjusted agent, conductive particle, ionic conductivity compound, dispersant, bridging agent etc.
(electroconductive polymer)
So long as main chain is got final product by the organic polymer that common rail system constitutes, there is not particular restriction as electroconductive polymer of the present invention.For example: polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyacetylene class and derivative thereof, poly-inferior benzene class and derivative thereof, polyphenylene 1, inferior vinyl of 2-and derivative thereof, polyaniline compound and derivative thereof, metacetaldehyde class and derivative thereof, poly-1,2-ethenylidene thiophene-based and derivative thereof, and these copolymer 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-carboxyethyl) pyrroles, poly-(3-methoxyl group) pyrroles, poly-(the own oxygen base of 3-) pyrroles, poly-(the own oxygen base of 3-methyl-4-) pyrroles waits the polypyrrole class; Polythiophene, poly-(3-methyl) thiophene, poly-(3-hexyl) thiophene, poly-(3-hydroxyl) thiophene, poly-(3-methoxyl group) thiophene, poly-(the own oxygen base of 3-) 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-dihydroxy) thiophene, poly-(3, the 4-dimethoxy) poly-(3, the 4-diethoxy) thiophene thiophene),, poly-(3,4-two own oxygen bases) 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 dihydroxy) 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 effect of oxidant or catalyst, change into electroconductive polymer from the 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 oxidant, iron chloride (III), ferric sulfate (III), copper chloride (II), p-methyl benzenesulfonic acid iron transistion metal compounds such as (III), silver oxide, cesium oxide metal oxides such as (Se), hydrogen peroxide, peroxide such as ozone, organic peroxides such as peroxidating 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 oxidant or oxidation polymerization catalyst 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 ethers ethylene glycol vinegar, dialkyl ethers propylene glycol vinegar, poly-dialkyl ethers ethylene glycol vinegar, poly-dialkyl ethers 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, triethylene glycol 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 oxidant or catalyst and polyanion.Can obtain fine solubility and conductivity at the electroconductive polymer that contains polymerization under the polyanion.
(polyanion)
As polyanion so long as side chain has the carboxylic acid group, sulfonic group, sulfate, the macromolecule of phosphate can use.Then requiring as main chain is that following material is formed: the polyalkylene compound that main chain is made of repeatedly methylene; Main chain contains the poly-alkenylene compound of the component unit formation of vinyl, poly-vinegar resin, poly-phthalein polyimide resin, poly-phthalimide resin, fluororesin, vinyl, epoxy resin, xylene resin, aramid resin, polyurethane are resin, melamine resin, 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 obtain copolymer 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 acrylic acid etc.Can enumerate as other polymerizable monomers: replace or unsubstituted vinyl compound, the substitutional crylic acid compound, replace or unsubstituted styrene, replace or unsubstituted vinylamine, the heterocyclic compound that contains unsaturated group, replace or unsubstituted propylene phthalein amines, 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 silicyl styrene arbitrarily, arbitrarily 5-substituted phenol compounds 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 benzene sulfonic acid with and salt, poly-sulfonic acid vinegar resin with and salt, poly-sulfonic acid phthalimide resin with and salt etc.
As the cation of polyanionic salt for example: ammonium salt, tetramethyl ammonium, tetraethyl ammonium salt, the tetrapropyl ammonium salt, 4-butyl ammonium, tetrahexyl ammonium salt, trimethyl ethyl ammonium salt, the trimethylphenyl ammonium salt, triethyl group phenyl ammonium salt, trimethylbenzene idol phthalein ammonium salt, 4 grades of ammonium salts such as trimethyl octyl group ammonium salt, metal cation salt, imidazole-like ionic salt, pyridines ion salt etc.From the preferred cationic nitrogenous of cationic electric stability.
The mean molecule quantity of polyanion is 1,000～1,000,000 scope, preferred 5,000～800,000 scope.
The mass ratio of polyanion and electroconductive polymer (polyanion: electroconductive polymer) preferred 99:1～1:99, more preferably 95:5～20:80, most preferably 80:20～30:70.As long as in this scope, then conductivity 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 conductivity sometimes.
When containing ionic conductivity compound and ionic compound in the solid electrolyte of the present invention, can obtain excellent ion conveying function.Transmit the performance that can be able to improve solid electrolytic capacitor ESR and capacity by improving ion.
(ionic compound)
As long as ionic conductivity is arranged, there is not particular restriction as ionic compound.Known low molecular ion compound and macroion compound all can use.Preferably contain carboxyl 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.
Can example enumerate as anion: carboxyl 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 cation: ammonium salt, tetramethyl ammonium, tetraethyl ammonium salt, the tetrapropyl ammonium salt, 4-butyl ammonium, tetrahexyl ammonium salt, trimethyl ethyl ammonium salt, the trimethylphenyl ammonium salt, triethyl group phenyl ammonium salt, trimethylbenzene idol phthalein ammonium salt, 4 grades of ammonium salts such as trimethyl octyl group ammonium salt, metal cation salt, imidazole-like ionic salt, pyridines ion salt etc.From the preferred cationic nitrogenous of cationic electric stability.
Ionic compound can prepare solid electrolyte by adding in the conductive-polymer solution, can also be by after containing the electroconductive polymer film that ionic compound solution impregnation system is equipped with, and drying prepares.
As long as can dissolve or disperse ionic compound, there is not particular restriction as the solvent of ionic compound solution.For example can enumerate: water, N-methyl pyrrolidone (NMP), N, N '-dimethyl methyl phthalein amine (DMF), N, N '-dimethyl second phthalein amine (DMAc), dimethyl sulfoxide (DMSO) (DMSO), methylphenol, phenol, xylenol, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, hexane, benzene, toluene, formic acid, acetate, ethylene carbonate vinegar, propylene carbonate vinegar, dioxane, diethyl ether, dialkyl ethers ethylene glycol vinegar, dialkyl ethers propylene glycol vinegar, poly-dialkyl ethers ethylene glycol vinegar, poly-dialkyl ethers 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, triethylene glycol 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.
When ionic compound makes an addition in the conductive-polymer solution, the mass ratio of ionic compound and electroconductive polymer (ionic compound: electroconductive polymer) preferred 1:99～90:10, more preferably 10:90～70:30.
(ionic conductivity compound)
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, acrylic, 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 conductivity of ionic compound with methods such as adding solvent or additive.Do not impose any restrictions at this.
The mass ratio of ionic conductivity compound and electroconductive polymer (ionic conductivity compound: electroconductive polymer) preferred 20:80～90:10, more preferably 50:50～90:10.
(dopant, conductivity is adjusted agent)
For the conductivity that improves above-mentioned electroconductive polymer can the mixing and doping agent, the conductivity adjustment
, conductivity is adjusted the performance that film forming is adjusted in agent in addition.
As long as can produce redox reaction with electroconductive polymer, do not limit electron acceptor or electronics and supply and body as dopant.For example: halogen compound, lewis acid, Bronsted acid etc.Can enumerate chlorine, iodine, lodine chloride, fluorine iodine etc. as halogen compound.Lewis acid can be enumerated phosphorus pentafluoride (PF
5), arsenic pentafluoride (AsF
5), boron trifluoride (BF
3), boron chloride (BCl
3) etc.Can enumerate as Bronsted acid: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluoboric acid, inorganic acids such as hydrofluoric acid, organic carboxyl acid, organic acids such as organic sulfonic acid, organic cyanogen compound etc.
Content as dopant is the mol ratio (dopant: electroconductive polymer) preferred 0.1:1～10:1, more preferably 0.5:1～7:1 of electroconductive polymer.When mol ratio is lower than this scope, then can not obtain sufficient conductivity sometimes.When mol ratio is higher than this scope, then can not obtain sufficient conductivity sometimes.
Adjust agent as conductivity and can use hydroxy-containing compounds, carboxylated compound (organic acid) (COOH) contains amino-compound, the amino-contained aromatic compound contains carbonyl (CO) compound, contains the acetify compound, contain ammonia vinegar based compound, contain ether compound, amide compound contains imide compound, contain acyclic compound, contain epoxy compounds, silicon-containing compound, fluorochemical 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, triethylene glycol butyl ether, butoxy triethylene glycol ether, oxeye alcohol, arabitol, 3-amino-1, the 2-propylene glycol, sweet mellow wine, glycol, diethylene glycol (DEG), triethylene glycol, poly-glycol, glycerine, diglycerol, polyglycereol, sorbierite, pentaerythrite, bipentaerythrite, 3-methoxyl group-1, the 2-propylene glycol, allitol, xylitol, galactitol, galactolipin, arabinose, glucose, monose, disaccharides, polysaccharide, galacturonic acid, gluconic acid, the DL-hydroxysuccinic acid, glutinous acid, gulonate, different VC acid, oxalic acid, malic acid, diacid ammonium, vitamin c class, tartaric acid, D-dibenzoyl tartaric acid, heptonic acid and these hydrochlorate, glucosamine, dioxane, diethyl ether, dialkyl ethers ethylene glycol vinegar, dialkyl ethers propylene glycol vinegar, poly-dialkyl ethers ethylene glycol vinegar, poly-dialkyl ethers propylene glycol vinegar, imidazoles, dihydroxy benzenes, trihydroxy benzene, dihydroxy naphthlene, trihydroxynaphthalene, isophthalic acid, SO 3 sulfonated M-phthalic acid, sour methyl esters, propenyl, the ethene imidazoles, vinylpyrrolidone, ethene dimethyl sulfoxide (DMSO), vinylpyridine, acrylonitrile (AN), N hydroxymethyl acrylamide (N-MAM), acrylic acid amides, acrylic acid hydroxyl phthalein amine (HEAA), acrylic acid (AA), propylene phthalein amine, N,N-DMAA, the ethoxy acrylamide, hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA), hydroxy propyl methacrylate, hydroxy propyl methacrylate (HPMA), acrylic acid hydroxy butyl ester (HBA), trimethylolpropane triacrylate (TMPTA), trimethylol-propane trimethacrylate (TMPTMA), vinyl sulfonic acid and vinyl sulfonate, styrene sulfonic acid and styrene sulfonate, acrylic acid vinyl sulfonic acid and acrylic acid vinyl sulfonate, first for allyl sulfonic acid and first for allyl sulfonate, methyl allyloxy benzene sulfonic acid and methyl allyloxy benzene sulfonate, vinylidenefluoride, hexafluoropropylene etc.
Conductivity is adjusted mass ratio (the conductivity 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 conductivity and solvent solubility are all high, when mass ratio is lower than this scope, then can not obtain the tendency of sufficient conductivity and film forming sometimes.When mass ratio is higher than this scope, then can not obtain sufficient conductivity sometimes.
(electroconductive particle)
Can add electroconductive particle arbitrarily in the solid electrolyte of the present invention, for example can enumerate: carbon particle, graphite particle, carbon fiber, carbon nano-tube as electroconductive particle, fullerene (fullerene), copper, nickel, silver, gold, tin, iron, metallics such as aluminium, metal acidulants particle, metallic fiber etc.Wherein preferred use is added can improve conductivity on a small quantity, and the carbon fiber of favorable dispersibility, graphite particle, carbon nano-tube, fullerene (fullerene).In addition, carbon particle, graphite particle, carbon fiber, the such material with carbon element of carbon nano-tube has reduction, has the effect of the electroconductive polymer deterioration that anti-block causes, so preferred.Replaceable any functional group on this material with carbon element.For example can enumerate: carbon particle, porous carbon particle, active carbon, graphite particle, porous graphite, graphite flake (comprising hand chair form armchair and sawtooth pattern 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, hydrosulphate, oxide 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.
Solid electrolyte of the present invention also can contain other compositions as required.For example to adjust film forming, film-strength 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 mixed and disperse to use any thermosetting resin, thermoplastic resin, photo-curable resin relatively.
As its object lesson of resin as poly-vinegar resinoid, poly-phthalimide resinoid, poly-phthalein amine resins, poly-fluorine-type resin, polythylene resin, epoxylite, the xylene resin, polyethylene glycols, aromatic species polyamide resin, polyurethane is a resin, poly-vein system resin, melamine resinoid, the 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 mix dispersion and can use any defoamer, nertralizer, antioxidant, surfactant, coupling agent, conductive fillers etc. do not have particular restriction.
Another object of the present invention is by using above-mentioned solid electrolyte, a kind of solid electrolytic capacitor with excellent ESR property being provided.And under hot environment, also can keep the performance of solid electrolytic capacitor.
(solid electrolytic capacitor)
Example to solid electrolytic capacitor of the present invention describes below.
Solid electrolytic capacitor of the present invention has: by the anode bodies that metal porous body is made, be formed at the dielectric layer that constitutes on the described metal surface, and the solid electrolyte layer between dielectric layer and the cathode, and cathode,
In the described solid electrolyte layer, have at least one deck to comprise by electroconductive polymer and polyanion, and boiling point more than 150 degree ionic compound and the solid electrolyte formed.The ionic compound solution of this solid electrolyte by containing this ionic compound with contain electroconductive polymer and polyanion with and after the electroconductive polymer film of salt contacts, form through removing a part or most solvent.Can add dopant as required, resinous principle is arranged, conductivity is adjusted agent, conductive particle, ionic conductivity compound, dispersant, bridging agent etc.
(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 the metal of the employed valve action of capacitor anode, tantalum (Ta), niobium (Nb).Can use oxidation film or organic dielectric film as the dielectric layer on the metal surface.The preparation method of oxidation film dielectric layer: can carry out after etching and processing increases its surface area aluminium foil, its surface be carried out the method for oxidation processes; And to the tantalum particle, the sintered body surface of niobium particle is carried out oxidation processes 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 dielectric layer of solid electrolytic capacitor, use infusion process, method such as spraying process or print process coating (coating) conductive-polymer solution, then with solvent seasoning, on the dielectric layer surface, form the conducting film that contains electroconductive polymer, obtain conductive polymer coated film.Ionic compound can be by after containing the conductive polymer coated film that ionic compound solution impregnation system is equipped with, and drying is annotated and obtained solid electrolyte layer in the conductive polymer coated film.
When solid electrolytic capacitor of the present invention is wound capacitor, also need have electrolytic paper.Electrolytic paper is located between the dielectric layer and cathode on the described metal surface.Solid electrolyte layer, through the dipping conductive-polymer solution after with solvent seasoning, formation contains the conducting film of electroconductive polymer, ionic compound can be by after containing the conductive polymer coated film that ionic compound solution impregnation system is equipped with, and drying is annotated and obtained solid electrolyte layer in the conductive polymer coated film.
Electric conductor as solid electrolyte layer can use aforesaid solid electrolyte and aforesaid electroconductive polymer etc.
(solid electrolytic paper)
As the solid electrolytic paper of solid electrolytic capacitor of the present invention, can use the solid electrolytic paper of known solid electrolytic capacitor not have particular restriction.
(cathode)
As the cathode of solid electrolytic capacitor of the present invention, can use electroconductive polymer, carbon, silver, aluminium, copper, nickel and these mixture etc.The preparation method can prepare with electric conductor paper tinsel or coating, does not have particular restriction.
Beneficial effect
Solid electrolytic capacitor of the present invention is filmed by using above-mentioned solid electrolyte, has high static capacity, the excellent properties of low ESR etc.And the static capacity of solid electrolytic capacitor of the present invention and ESR, under hot environment, also can keep its excellent performance.
(implementation example)
Preparation object lesson to solid electrolyte 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 polystyrolsulfon acid aqueous solution of the 30wt% of 50g and the ammonium persulfate of 10g, the ferric sulfate of 1g dissolve in 500ml water, stir 18 hours.
Remove residual ion in the solution with spent ion exchange resin after the WITH AMMONIA TREATMENT, through polystyrolsulfon acid ammonia-poly-(3,4-ethylene dioxy base) the thiophene aqueous solution that obtains navy blue 1.6wt% after the dispersion treatment.
The polystyrolsulfon acid of the 1.6wt% of the 10g that obtains-poly-(3,4-ethylene dioxy base) thiophene aqueous solution, the hydroxy-ethyl acrylate of 0.3g, the ammonium adipate of 0.1g, the N-N-methyl-2-2-pyrrolidone N-of 0.3g mixes stirring, obtains the navy blue solid electrolyte solution.In 120 ℃ of degree baking ovens, carry out drying, the solid electrolyte that obtains.Estimate the conductivity of solid electrolyte, its result is as shown in table 1.
Embodiment 2
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 10g of embodiment 1 preparation, the hydroxy-ethyl acrylate of 0.3g, the N-N-methyl-2-2-pyrrolidone N-of 0.3g mix and stir, and obtain the navy blue solid electrolyte solution.In 120 ℃ of degree baking ovens, carry out drying, the electroconductive polymer film that obtains.
Then, with the electroconductive polymer film in the ammonium adipate water-ethylene glycol solution of 10wt% quiet soak 5 minutes after, carry out drying, the solid electrolyte that obtains at 120 ℃ of degree in the baking ovens.Estimate the conductivity of solid electrolyte, its result is as shown in table 1.
Embodiment 3
The electroconductive polymer film that obtains with embodiment 2 in the ammonium benzene sulfonate aqueous solution of 10wt% quiet soak 5 minutes after, in 120 ℃ of degree baking ovens, carry out drying, the solid electrolyte that obtains.Estimate the conductivity of solid electrolyte, its result is as shown in table 1.
Embodiment 4
The electroconductive polymer film that obtains with embodiment 2 is at the benzene sulfonic acid-1 of 10wt%, in the 3-methylimidazole aqueous solution quiet soak 5 minutes after, in 120 ℃ of degree baking ovens, carry out drying, the solid electrolyte that obtains.Estimate the conductivity of solid electrolyte, its result is as shown in table 1.
Comparative example 1
Have only the same method evaluation with polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 5g of embodiment 1 preparation and embodiment 1, its result is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Conductivity (S/cm) | 120 | 140 | 170 | 190 | 1.5 |
Embodiment 5
(preparation of winding capacitance semi-finished product sub-prime)
With the anode foils that changes into processing of guide pin on the fourth, the negative foil roll coiled specification 25V-150 μ F winding capacitance semi-finished product sub-prime of guide pin on solid electrolytic paper and the fourth.
(preparation of solid electrolyte solution)
With polystyrolsulfon acid-poly-(3,4-ethylene dioxy base) thiophene aqueous solution of the 1.5wt% of the 10g of embodiment 1 preparation, the hydroxy-ethyl acrylate of 0.3g, the N-N-methyl-2-2-pyrrolidone N-of 0.3g mix and stir, and obtain the navy blue solid electrolyte solution.
(making of solid electrolytic capacitor)
After being impregnated in the winding capacitance semi-finished product sub-prime with the vacuum decompression method, carry out drying at 120 ℃ of degree in the baking ovens to solid electrolyte solution, the dipping that uses the same method then/drying 2 times obtains containing the sub-prime of electroconductive polymer film.After flooding the ammonium adipate water-ethylene glycol 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.(capacity, ESR), its result is as shown in table 2 for the performance of evaluation solid electrolytic capacitor.
Embodiment 6,7
The ammonium adipate water-ethylene glycol solution of the 10wt% of embodiment 5 is changed to the ammonium benzene sulfonate aqueous solution (embodiment 6) of 10wt% and the benzene sulfonic acid-1 of 10wt% respectively, and the 3-methylimidazole aqueous solution (embodiment 7) method similarly to Example 5 obtains solid electrolytic capacitor.Method evaluation similarly to Example 5, its result is as shown in table 2.
(comparative example 2)
After the sub-prime that the sub-prime that obtains containing the electroconductive polymer film with embodiment 5 will contain the solid solid electrolyte with shell and Jiao Gai seals, obtain solid electrolytic capacitor.The method evaluation same with embodiment 5, its result is as shown in table 2.
Table 2
More than as shown in table 1, the conductivity by adding the solid electrolyte that conductivity adjusts agent and ionic compound among the embodiment 1 to embodiment 4 is than not adding solid electrolyte up to more than 60 times.
As shown in table 2, use the solid electrolytic capacitor of the solid electrolyte contain ionic compound to compare and have higher capacity and hang down ESR, and these performances are under hot environment, also all higher sustainment rate with the solid electrolytic capacitor that does not contain ionic compound.
Claims (10)
1. solid electrolyte, it is characterized in that comprising electroconductive polymer and polyanion or/and salt, and ionic compound, this electroconductive polymer is by polypyrrole class and derivative thereof, polythiophene class and derivative thereof, polyaniline and derivative thereof, metacetaldehyde class and derivative thereof, poly-1,2-ethenylidene thiophene-based and derivative thereof, at least a in the copolymer of polyethylene click and derivative thereof and these compounds; This polyanion contains carboxyl, at least a functional group in the sulfonic group; This ionic compound is by anion and cation composition, and this cationic part is a cationic nitrogenous at least.
2. solid electrolyte according to claim 1, wherein said ionic compound are the ionic liquid ionic compound.
3. according to claim 1,2 described solid electrolytes wherein contain carboxyl, hydroxyl, and cyano group, amide groups, fluorine-based, oxyl, amino, the ionic conductivity compound of at least a functional group in the ether.
4. solid electrolyte according to claim 3, wherein said ionic conductivity compound is an ether compound, at least a in the glycols compound.
5. according to a kind of solid electrolyte described in the claim 1～4, also contain dopant, conductivity is adjusted bond, resinous principle, at least a in the conductive particle.
6. solid electrolyte, it is characterized in that comprising electroconductive polymer and polyanion or/and salt, and ionic compound, the ionic compound solution of this solid electrolyte by containing ionic compound forms through removing a part or most solvent with after the electroconductive polymer film that contains electroconductive polymer and polyanion or/and salt contacts.
7. solid electrolyte according to claim 6 contains the ionic conductivity compound in the wherein said ionic compound solution, dopant, and conductivity is adjusted bond, resinous principle, at least a in the conductive particle.
8. solid electrolytic capacitor is characterized in that having at least anode bodies, dielectric layer, and solid electrolyte layer, and cathode in the described solid electrolyte layer, have at least 1 layer to be a kind of solid electrolyte described in the claim 1～7.
9. the solid electrolytic capacitor preparation method is characterized in that having the program for preparing solid electrolyte layer at least; The ionic compound solution that contains ionic compound with contain the program that the electroconductive polymer film contacts; Remove the program of desolvating.
10. a kind of solid electrolytic capacitor preparation method according to claim 9 also contains dopant in the wherein said ionic compound solution, and conductivity is adjusted bond, resinous principle, conductive particle, at least a in the ionic conductivity compound.
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