CN102612722A - Solid electrolytic capacitor and method for producing same - Google Patents
Solid electrolytic capacitor and method for producing same Download PDFInfo
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- CN102612722A CN102612722A CN2010800459648A CN201080045964A CN102612722A CN 102612722 A CN102612722 A CN 102612722A CN 2010800459648 A CN2010800459648 A CN 2010800459648A CN 201080045964 A CN201080045964 A CN 201080045964A CN 102612722 A CN102612722 A CN 102612722A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
Abstract
Disclosed is a solid electrolytic capacitor having heat-resistance and electrical properties that are more excellent and that has a high capacitance and a low ESR. Further disclosed is a method for producing same. [1] The solid electrolytic capacitor is a thiophene derivative having a heteroatom-containing cyclic substituent group and is characterized by containing as a solid electrolyte the molecule obtained by polymerizing a compound having an alkyl substituent group on the heteroatom-containing cyclic substituent group. [2] The method for producing the solid electrolytic capacitor has a step wherein the molecule described in [1] mentioned above is formed on a valve-action metal on which a dielectric oxide film has been formed.
Description
Technical field
The present invention relates to a kind of solid electrolytic capacitor (solid state electrolytic capacitor), relate to a kind of excellent solid electrolytic capacitor and manufacturing approach thereof of electrical characteristics that possesses the electroconductive polymer layer that shows high conductivity as solid electrolyte layer more in detail with solid electrolyte layer.
Background technology
The solid electrolyte that is used in solid electrolytic capacitor forms and to use that material is known to be had with the inorganic conductive property material or 7,7 as representative such as manganese dioxide, 8; 8-four cyano quinoline bismethane (7; 7,8,8-tetracyanoquinodimethane) the organic conductive material of (TCNQ) complex compound etc.
And, form with the excellent conductive polymer material of material as the solid electrolytic capacitor of solid electrolyte use extensively by practicability than this based solid electrolyte with conductivity.
In this conductive polymer material, with 3, the 4-Ethylenedioxy Thiophene (3,4-ethylenedioxythiophene) be widely known by the people for the electroconductive polymer of monomer (monomer) polymerization by (following brief note is [EDOT]).
This EDOT is steady because of the reaction speed of polymerization, and formation and the excellent electroconductive polymer layer of the adherence of the dielectric oxide film (dielectricoxidefilm) of anode form material of great use so be used as the solid electrolyte layer of solid electrolytic capacitor.
But; E-machine in recent years be asked to towards more economize electrification, high-frequencyization is corresponding, in being used in the solid electrolytic capacitor of such e-machine, also is asked to the further raising of the electrical characteristics of small-sized high capacity and low ESR (Equivalent Series Resistance) (following brief note is [ESR]) change etc.
The electrical characteristics of solid electrolytic capacitor exist with ... employed solid electrolyte widely and form material category or formation method, and surpass the exploitation of the good electroconductive polymer monomer of well-known EDOT in the past or the formation method of new solid electrolyte layer is expected.
Among this background; Known technology is known to be had with the polymer (polymer) of 3-alkyl-4-alkoxy thiophene (3-alkyl-4-alkoxythiophene) solid electrolytic capacitor as solid electrolyte; Reported through using this polymer, even can obtain the solid electrolytic capacitor (patent documentation 1) that high frequency region also has good electrical characteristics.
And, proposed to use polymerization to have the solid electrolytic capacitor of the polymer that obtains with the stretching alkyl dioxy base thiophene (alkylenedioxythiophene) derivative of the substituted position of alkoxyl as solid electrolyte.
Through adopting this polymer, can suppress to residue in polymerization in the polymer with the crystallization of oxidant, can reduce the leakage current (leakage current) (patent documentation 2) of the solid electrolytic capacitor that obtains.
Patent documentation 1: TOHKEMY 2001-332453 communique
Patent documentation 2: TOHKEMY 2004-096098 communique
Summary of the invention
But, be difficult to only rely on the polymer that is disclosed in above-mentioned document and obtain enough electrical characteristics and thermal endurance, require to have the electrical characteristics and the stable on heating raising of solid electrolytic capacitor further.
On the other hand; Solid electrolytic capacitor is in order to make the direct capacitance high capacity; Have reel or lamination (laminate) through etching (etching) expansion faceization aluminium foil and be used in the paper tinsel type of anode component, and with the metal particle sinter molding and form porous body and obtain jumbo sinter molding element type.The sinter molding element type is to be purpose with the high capacity, and the particle diameter of metal particle is more and more by micronize, and its CV long-pending (amassing of the direct capacitance of every 1g sinter molding element and voltage) reaches more than the 100000 μ FV/g.
And in recent years based on high performance, polypyrrole (polypyrrole) or PEDOT (polyethylenedioxythiophene: gather the dioxoethyl thiophene) are used in solid electrolyte.This compounds is through chemical oxidising polymerisation (chemical oxidative polymerization) or electrolysis polymerization (electropolymerization) polymerization; But the space of porous sintering profile member has the tendency of miniaturization, and polymerization filling polypyrrole or PEDOT are very difficult in this space.
The object of the invention is to provide a kind of except the more excellent electrical characteristics that show high direct capacitance and low ESR, also has good stable on heating solid electrolytic capacitor and manufacturing approach thereof concurrently.
The result of the wholwe-hearted research of present inventors finds, comprises so that the high molecular solid electrolytic capacitor that the compound polymerization of representing through formula [1] obtains can reach the object of the invention as solid electrolyte, thereby, accomplish the present invention.
Also promptly, the present invention is as follows:
First invention is a kind of solid electrolytic capacitor, it is characterized in that,
Comprise so that the macromolecule that the compound polymerization of representing through formula [1] obtains as solid electrolyte.
In above-mentioned general formula [1], R
1It is the alkyl of the straight or branched of expression carbon number 1～6.Z is independent separately expression oxygen atom or sulphur atom.
Second invention is a kind of solid electrolytic capacitor, it is characterized in that,
Comprise so that the macromolecule that at least one polymerization of the compound through formula [2] and [3] expression obtains as solid electrolyte.
The 3rd invention wherein, comprises so that the macromolecule that the compound polymerization of representing through above-mentioned general formula [2] obtains as solid electrolyte for being recorded in the solid electrolytic capacitor of second invention.
The 4th invention is for being recorded in the solid electrolytic capacitor of second invention, and wherein, the porousness formed body that obtains with sintered valve effect metal particle comprises as anode:
Be formed at the dielectric oxide film on aforesaid anode surface;
Comprise the high molecular solid electrolyte that at least one polymerization of compound that will be through above-mentioned general formula [2] and [3] expression obtains in aforementioned dielectric oxide film surface; And
Comprise the carbon-coating that is formed at aforementioned high molecular surface and the negative electrode of silver layer.
The 5th invention is for being recorded in the solid electrolytic capacitor of the 4th invention, is used in the aforementioned valve metals particulate of sintering and the valve metals particulate of the porousness formed body that obtains comprises at least one of tantalum metal particle and niobium metal particulate,
The CV of per unit mass is long-pending to be shown more than the 20000 μ FV/g.
The 6th invents to a kind of manufacturing approach of solid electrolytic capacitor, it is characterized in that,
Have: the macromolecule that the compound polymerization through formula [1] expression will be obtained is formed at the operation on the valve metals that is formed with dielectric oxide film.
In above-mentioned general formula [1], R
1It is the alkyl of the straight or branched of expression carbon number 1～6.Z is independent separately expression oxygen atom or sulphur atom.
The 7th invents to a kind of manufacturing approach of solid electrolytic capacitor, it is characterized in that,
Have: the macromolecule that at least one polymerization of the compound through formula [2] and [3] expression will be obtained is formed at the operation on the valve metals that is formed with dielectric oxide film.
The 8th invention is the manufacturing approach that is recorded in the solid electrolytic capacitor of the 6th invention or the 7th invention, and wherein, the operation that aforementioned macromolecule is formed on the valve metals that is formed with dielectric oxide film comprises:
Make in liquid phase (A) be selected from by the group that forms through the compound of above-mentioned general formula [1], [2] and [3] expression at least one, (B) alloy (dopant) and (C) the oxidant operation that contacts and carry out polymerization.
The 9th invention is for being recorded in the manufacturing approach of solid electrolytic capacitor of the 8th invention, wherein, aforementioned (B) alloy and (C) oxidant use and have (B) alloy and (C) both compound of character of oxidant.
The tenth invention is the manufacturing approach that is recorded in the solid electrolytic capacitor of the 9th invention; Wherein, Have aforementioned (B) alloy and (C) both compound of character of oxidant be organic sulfonic acid molysite (organic sulfonic acid ferric salt), aforementioned liquid phase comprises the organic sulfonic acid molysite with the scope of 40～70 weight %
The 11 invention is the manufacturing approach that is recorded in the solid electrolytic capacitor of the 7th invention, and wherein, the porousness formed body that obtains with sintered valve effect metal particle comprises as anode:
Form the operation of dielectric oxide film on the aforesaid anode surface;
The macromolecule that at least one polymerization of compound through above-mentioned general formula [2] and [3] expression will be obtained is formed at the operation on the anode that is formed with aforementioned dielectric oxide film; And
Form the operation of the negative electrode that comprises carbon-coating and silver layer on aforementioned high molecular surface.
The 12 invention is the manufacturing approach that is recorded in the solid electrolytic capacitor of the 11 invention, and wherein, the operation that aforementioned macromolecule is formed on the anode that is formed with aforementioned dielectric oxide film comprises:
Make in liquid phase (A) be selected from by at least one of the group that forms through the compound of above-mentioned general formula [1], [2] and [3] expression and (C) oxidant contact and carry out the operation of chemical oxidising polymerisation.
The effect of invention
According to the present invention, can provide that direct capacitance is high, ESR is low and the solid electrolytic capacitor of excellent heat resistance.
And; Because of using as solid electrolyte so that under the high molecular situation that at least one polymerization of the compound of representing through formula [2] and [3] obtains; The polymerization speed of such monomer (polymerization rate) relatively steadily, the space of the porousness formed body that obtains so can be filled in fully that sintering has the valve metals particulate of fine porous matter.
In view of the above, can provide that direct capacitance is high, ESR is low and the solid electrolytic capacitor of excellent heat resistance.
Description of drawings
Fig. 1 is that the substituent carbon number of getting EDOT is a transverse axis, gets polymerization speed (second) and is the chart of the longitudinal axis (embodiment 4～6 and comparative example 1～2).
Fig. 2 is that the substituent carbon number of getting EDOT is a transverse axis, gets ESR (m Ω) and is the chart of the longitudinal axis (embodiment 7～9, comparative example 4,7).
Fig. 3 is the constructed profile in order to the structure of the explanation solid electrolytic capacitor relevant with embodiments of the invention 10.
The explanation of Reference numeral
1: comparative example 3
2: embodiment 4
3: embodiment 5
4: embodiment 6
5: comparative example 2
6: comparative example 7
7: embodiment 7
8: embodiment 8
9: embodiment 9
10: comparative example 4
11: anode
12: dielectric oxide film
13: solid electrolyte
14: graphite linings
15: silver-colored paste layer
16: positive wire
17: cathode wire
18: package resin
19: the conductivity solid
Embodiment
Below at length explain to the present invention.
The present invention is a kind of solid electrolytic capacitor, comprises so that the macromolecule that the compound polymerization of representing through formula [1] obtains as solid electrolyte.
In above-mentioned general formula [1], R
1It is the alkyl of the straight or branched of expression carbon number 1～6.Z is independent separately expression oxygen atom or sulphur atom.
Carbon number is 1～6 the straight chain shape or the alkyl of branched; For example can enumerate: methyl, ethyl, n-pro-pyl (n-propyl), isopropyl (isopropyl), normal-butyl (n-butyl), isobutyl group (isobutyl), sec-butyl (sec-butyl), the tert-butyl group (t-butyl), n-pentyl (n-pentyl), isopentyl (isopentyl), 1-methyl butyl, 1-ethyl propyl, 1; 2-dimethyl propyl, 1,1-dimethyl propyl, neopentyl (neopentyl), n-hexyl (n-hexyl) etc.
In such alkyl carbon number be 1～3 straight chain shape or branched alkyl more preferably, concrete going up is methyl, ethyl, n-pro-pyl, isopropyl, more preferably methyl, ethyl most preferably are methyl.
Carbon number surpasses the situation of the alkyl of 6 straight or branched, and the polymerisation reactivity of resulting compound reduces, and is difficult to obtain polymer.
Preferred the enumerating of compound through aforementioned formula [1] expression: 2-methyl-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-methyl-EDOT) (2-methyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-methyl-EDOT)); 2-ethyl-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-ethyl-EDOT) (2-ethyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-ethyl-EDOT)); 2-propyl group-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-propyl group-EDOT) (2-propyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-propyl-EDOT));
2-isopropyl-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-isopropyl-EDOT) (2-isopropyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-isopropyl-EDOT));
2-butyl-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-butyl-EDOT) (2-butyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-butyl-EDOT)); 2-amyl group-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-amyl group-EDOT) (2-pentyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-pentyl-EDOT)); 2-hexyl-2,3-dihydro-thiophene be [3,4-b]-1 also, 4-dioxin (2-hexyl-EDOT) (2-hexyl-2,3-dihydrothieno [3,4-b]-1,4-dioxine (2-hexyl-EDOT)) etc.
The macromolecule that compound polymerization through above-mentioned general formula [1] expression is obtained can show high conductivity, thermal stability (thermostability) excellence.
Be used in aforesaid compound of the present invention and well-known electroconductive polymer monomer, for example EDOT relatively is enhanced for polymerization speed.
Also promptly, although polymerization speed relaxes than EDOT, because of being rich in polymerism, so may penetrate into polymerization till the hole depth of valve metals with porous matter and complicated shape.
Therefore, the macromolecule that is used in compound of the present invention becomes the conductive polymer material of the solid electrolyte that is particularly suitable for solid electrolytic capacitor.
In above-claimed cpd, use at least one the situation of compound of formula [2] and [3], can obtain the particularly solid electrolytic capacitor of ESR characteristic and excellent heat resistance.
Macromolecule that at least one polymerization of compound through above-mentioned general formula [1]～[3] expressions obtains can be obtained through the polymerization shown in following etc.
For example, also can obtain macromolecule through using oxidant chemical oxidising polymerisation above-claimed cpd, and, also can obtain macromolecule through electrochemical oxidation polymerization.
Aforementioned oxidant in the chemical oxidising polymerisation can be enumerated: the halide of iodine, bromine, bromine iodide, chlorine dioxide, acid iodide, periodic acid, chlorous acid etc.; The metal halide of antimony pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminium chloride, molybdenum chloride etc.; High chemical valence status transition metal ion or its salt of permanganate, bichromate, chromic anhybride (chromic anhydride), molysite, mantoquita etc.; The Bronsted acid (protic acid) of sulfuric acid, nitric acid, TFMS (trifluoromethanesulfonic acid) etc.; The oxygen compound of sulfur trioxide, nitrogen dioxide etc.; The peroxy acid and the salt of hydrogen peroxide, ammonium persulfate (ammonium persulfate), sodium perborate (sodium perborate) etc.; Heteropoly acid of phosphomolybdic acid, phosphotungstic acid, P-Mo-Wo acid etc. (heteropolyacid) and salt etc.
And electrochemical oxidation polymerization can be enumerated at least one of compound that will be through above-mentioned general formula [1]～[3] expressions and electrolyte that alloy is dissolved in solvent, the method for polymerization etc. through electrolytic oxidation.
Above-mentioned alloy for example can be enumerated: the halide ion of the halide ion of iodine, bromine, chlorine etc., phosphorus hexafluoride, arsenic hexafluoride, antimony hexafluoride, tetrafluoride boron, mistake chloric acid etc.; The alkyl of methanesulfonic acid, dodecyl sodium sulfonate etc. replaces organic azochlorosulfonate acid ion; The ring-type azochlorosulfonate acid ion of camphorsulfonic acid ion etc.; The alkyl of benzene sulfonic acid, p-methyl benzenesulfonic acid, DBSA, benzenedisulfonic acid etc. replaces or does not have substituted benzene sulfonic acid or a disulfonic acid ion; Replace 1～4 2-naphthalene sulfonic acids and 1, the alkyl of the sulfonic naphthalene sulfonic acids of 7-naphthalenedisulfonic acid etc. replaces or does not have a substitution ion; Rylnthracene sulfonin ion, anthraquinone sulfonic acid ion; The alkyl of alkyl biphenyl sulfonic acid (alkyl biphenyl sulfonic acid), biphenyl disulfonic acid (biphenyldisulfonic acid) etc. replaces or does not have a substituted biphenyl azochlorosulfonate acid ion; The macromolecule sulfonic acid ion of polystyrolsulfon acid, naphthalenesulfonateformaldehyde formaldehyde condensation body etc. etc.; The heteropoly acid ions of phosphomolybdic acid, phosphotungstic acid, P-Mo-Wo acid etc. etc. can be used as supporting electrolyte (supporting electrolyte) with such various salt and use.
Above-mentioned solvent can be enumerated: water; The ethers of oxolane (THF), dioxanes (dioxane), diethyl ether etc.; The ketone of acetone, butanone etc.; Dimethyl formamide (DMF), acetonitrile, benzonitrile, N-N-methyl 2-pyrrolidone N-(NMP), methyl-sulfoxide (DMSO), gamma-butyrolacton (GBL), propene carbonate (PC), carbonic acid are stretched the non-protonic solvent (aprotic solvent) of ethyl ester (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) etc.; The ester class of ethyl acetate, butyl acetate etc.; The nonaromatic chlorine compound series solvent of chloroform, carrene etc.; The nitro compound series solvent of nitre methane, nitroethane, nitre benzene etc.; The alcohols of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, ethylene glycol etc.;
The organic acid of formic acid, acetate, propionic acid etc. or this organic acid acid anhydrides (acetic anhydride (acetic anhydride) etc.) etc.
Above-mentioned solvent can use separately certainly, also can use with the mixed solvent of the plural number kind of mixing above-mentioned solvent.
Electrochemical polymerization can form macromolecule through electrolytic oxidation above-claimed cpd in above-mentioned electrolyte on anode.
Solid electrolytic capacitor of the present invention possesses and comprises polymerization at least one high molecular solid electrolyte layer that obtains through the compound of above-mentioned general formula [1]～[3] expressions, has direct capacitance height, good electrical characteristics that ESR is low.
In addition, compared to gathering 3 with known, (following brief note is [PEDOT] to 4-dioxoethyl thiophene.) as the solid electrolytic capacitor of solid electrolyte layer, thermal endurance improves significantly.
Though it is unclear clear and definite that solid electrolytic capacitor of the present invention shows the reason of low ESR; But can be thought of as: owing to the polymerization speed that is used in compound of the present invention is slower; Macromolecule after polymerization liquid often is penetrated in the dielectric oxide film forms possibility, so can form the higher solid electrolyte layer of adherence.
And; Inferred for because of causing as follows: the alkyl that generation is lacked with chain length owing to the macromolecule that obtains has the inductive effect (inductive effect) that is caused as substituting group; Electron distributions (electron distribution) enlarges (conjugated system (conjugated system) expansion) than PEDOT, its conductivity raising as a result.
Then, to the manufacturing approach explanation of solid electrolytic capacitor of the present invention.
The manufacturing approach of solid electrolytic capacitor of the present invention is characterized in that, has: the macromolecule that the compound polymerization through above-mentioned general formula [1] expression will be obtained is formed at the operation on the valve metals that is formed with dielectric oxide film.
Valve metals for example, can be used the alloy of aluminium, tantalum, titanium, niobium etc. or this dvielement, more preferably can enumerate aluminium, tantalum, niobium.
The form of such valve metals is metal forming or is that the sintered body etc. of the powder of principal component can be fit to use with this dvielement.
Above-mentioned valve metals form the method for dielectric oxide film can chemical liquids at adipic acid two ammoniums (diammonium adipate) aqueous solution etc. in through carrying out anodic oxidation, form dielectric oxide film on the valve metals surface.
Forming above-mentioned high molecular operation also can be for utilizing the method for above-mentioned chemical oxidising polymerisation, and can be for utilizing the method for electrolytic oxidation polymerization.
By the electrical characteristics of resulting solid electrolytic capacitor or easier this aspect of operation, form high molecular operation more preferably through chemical oxidising polymerisation.
Forming high molecular more preferably manufacturing approach through chemical oxidising polymerisation is to comprise following operation: through make at least one compound (A), alloy (B) and oxidant (C) contact through the compound of above-mentioned [1]～[3] expression in liquid phase, on valve metals, form macromolecule.
In liquid phase the method for this above-claimed cpd (A), alloy (B) and oxidant (C) contact can be enumerated:
1. adjustment mixes the solution of at least one compound (A), alloy (B) and the oxidant (C) of the compound of representing through above-mentioned [1]～[3], makes this solution contact valve metals through coating or dipping, obtains high molecular method;
2. prepare aforesaid compound liquid, prepare to contain the solution of alloy and oxidant in addition, make impregnation keep the valve metals coating or the dipping of above-claimed cpd liquid to be contacted with in the aforementioned oxidizing agent solution, obtain high molecular method;
3. aforesaid compound liquid coating or dipping are contacted with the valve metals that coating or impregnation keep containing the solution of alloy and oxidant, obtain the method for polymer etc.
These class methods are not limited especially.
Can form through the liquid stipulated time that keeps comprising the compound (A), alloy (B) and the oxidant (C) that are held on valve metals in set point of temperature in the high molecular method of formation on the valve metals.
Here, set point of temperature is meant and can selects arbitrarily 0 ℃ to 150 ℃ scope that the stipulated time is meant and can selects arbitrarily 1 minute to 24 hours scope.
Preferred mode in the manufacturing approach of solid electrolytic capacitor of the present invention can be enumerated both method of solution of compound of character with alloy (B) and oxidant (C) of using.
Both compound of character with alloy (B) and oxidant (C) is meant the oxidant of the anion component that comprises the alloy that becomes electroconductive polymer; Through using this oxidant that comprises the anion component of the alloy that becomes electroconductive polymer; When chemical polymerization; Anion component is taken into electroconductive polymer and is used as alloy performance function, can obtain the electroconductive polymer that conductivity is enhanced.
More preferably anion component can be enumerated: the organic acid ion of organic sulfonic acid ion, carboxylic acid ion etc., boron compound ion, phosphate cpd ion, mistake chlorate ions's etc. inorganic acid ion etc.
This oxidant that comprises anion component; Particularly suitable enumerating: organic acid iron (III) salt of iron (III) salt, benzene sulfonic acid iron or p-methyl benzenesulfonic acid molysite, the alkyl naphthalene sulfonic acid molysite etc. of the inorganic acid of iron chloride or mistake ferric chlorate (ferric perchlorate) etc., optimal organic sulfonic acid iron (III) salt of enumerating.
Make have (B) alloy and (C) oxidant both character compound dissolving solvent with the pure series solvent of methyl alcohol, ethanol, normal propyl alcohol (n-propanol), isopropyl alcohol (isopropanol), n-butanol (n-butanol), ethylene glycol etc. more preferably, more preferably can enumerate ethanol, n-butanol.
Particularly suitable in this compounds is the iron (III) that is dissolved with the above-mentioned organic sulfonic acid of 20 weight %～90 weight % at above-mentioned pure series solvent; More preferably be dissolved with the iron (III) of the above-mentioned organic sulfonic acid of 30 weight %～80 weight %, most preferably be the iron (III) of the above-mentioned organic sulfonic acid that is dissolved with 40 weight %～70 weight %.
Have (B) alloy of being dissolved into this concentration and (C) both compound of character of oxidant through use, can the macromolecule of conductivity and excellent in te pins of durability be formed at densely on the valve metals with complicated shape.
Below to the manufacturing approach of solid electrolytic capacitor of the present invention, enumerating the method for making the convoluted capacitor of aluminium is that concrete example is explained.
At first, after etching becomes the aluminium foil surface of anode and makes its matsurfaceization, connect positive wire, then in the aqueous solution of adipic acid two ammoniums etc., carry out chemical treatment (chemical conversion treatment), dielectric oxide film is formed.About embodiment of the present invention,, can obtain the big capacitor of direct capacitance, so more preferably through using the big paper tinsel of etching multiplying power (etching ratio).
In addition, between subtend cathode aluminum foil that connects cathode wire and above-mentioned anode aluminium foil, sandwich the dividing plate (separator) of Manila paper (manila paper) etc., be wound into cylindricly, then make the dividing plate carbonization, prepare convoluted capacitor element through heat treatment.
Secondly, on the anode foils of above-mentioned capacitor element, form the solid electrolyte layer that constitutes by electroconductive polymer.The method that this solid electrolyte layer is formed is that the method through dipping, coating, spraying etc. contains the liquid of the compound of at least one expression that comprises general formula [1]～[3] through the electroconductive polymer monomer to be dipped in capacitor element; Then, make its polymerization reaction and form solid electrolyte layer through the compound that makes oxidant contact impregnation.
In addition, make its impregnation oxidant earlier, make the method for its contact above-claimed cpd and polymerization then, perhaps make its quickly impregnation mixing above-claimed cpd and the solution of oxidant and the method for polymerization also can be suitable for, be not defined especially.
And chemical oxidising polymerisation is placed the stipulated time through compound, alloy and the oxidant that under 0～150 ℃ temperature, will in liquid phase, contact, and makes the solvent heat drying, carries out polymerization more preferably.Less than 0 ℃ of very difficult down polymerization reaction that produces, surpassing the situation that has capacitor specific characteristics to worsen under 150 ℃ the temperature.
Above-mentioned impregnation, heating process also can repeat plural number.
Through above-mentioned operation, can in the fine etch-hole of anode aluminium foil, form the solid electrolyte layer of abundant filled conductive property macromolecule layer.
Then, use epoxy resin that capacitor case is sealed, apply voltage and wear out (aging), can obtain solid electrolytic capacitor of the present invention.
Below, according to embodiment the present invention is described at length, but the present invention can not limited at all by embodiment.
In addition, [%] is expression [quality %] among the embodiment.And except specially appointed situation, direct capacitance (C) and dielectric loss (dielectric loss) (tan δ) are with frequency 120Hz, and equivalent series resistance (ESR) is then measured with frequency 100kHz.
And electric capacity impregnation rate is to represent the ratio of the direct capacitance of the capacitor element before the direct capacitance of the capacitor element after resulting solid electrolyte layer forms forms with the solid electrolyte layer of in 15% adipic acid, two aqueous ammoniums, measuring with percentage.
And, LC be the expression leakage current, be illustrated in apply rated voltage after, measure the galvanic value that flows to solid electrolytic capacitor after 60 seconds.
And withstand voltage (withstand voltage) is that expression applies voltages to the two ends of solid electrolytic capacitor, the voltage (V) the when direct current that flows to solid electrolytic capacitor surpasses 200mA.When in addition, applying voltage for made rise 1V and observation of voltage flow to the direct current of solid electrolytic capacitor in per 30 seconds from 15V.
Embodiment 1
[use 2-methyl-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-methyl-EDOT)]
The surperficial of etching aluminium foil and after making its matsurfaceization, connect positive wire through riveted joint, then in 10% adipic acid, two aqueous ammoniums, carry out chemical treatment with voltage 4V, form dielectric oxide film on the surface of aluminium foil.
Then; Between the subtend cathode aluminum foil that above-mentioned anode foils is connected with cathode wire, be used as dividing plate with the Manila paper of thickness 50 μ m and sandwich, be wound into cylindric; Then; With 400 ℃ of heat treatments of temperature 4 minutes, make the Manila paper carbonization, prepare capacitor element.The direct capacitance of resulting capacitor element in 15% adipic acid, two aqueous ammoniums is 650 μ F.
Secondly, prepare 3-dihydro-thiophene also [3 as the 2-methyl-2 that is used in polymeric compounds; 4-b]-1; (2-methyl-EDOT) and 50% p-methyl benzenesulfonic acid iron (p-toluenesulfonic acid ferric)/butanol solution as oxidant impregnated in both weight rates of blending with this capacitor element and become 1: 2.5 solution after 120 seconds, with 45 ℃ of heating 2 hours the 4-dioxin; With 105 ℃ of heating 35 minutes; With 125 ℃ of heating 1 hour, carry out chemical oxidising polymerisation, make and gather 2-methyl-EDOT (poly2-methyl-EDOT) and be formed in the capacitor element.
Then, use epoxy resin that this capacitor case is sealed, apply voltage 4V to the two poles of the earth and wear out, accomplish solid electrolytic capacitor.
[use 2-ethyl-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-ethyl-EDOT)]
Prepare the capacitor element that is over embodiment 1 same polymerization pre-treatment, except using 2-ethyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-ethyl-EDOT) replaces the 2-methyl-2 of embodiment 1 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) as being used in beyond the polymeric compounds, all the other are to handle with embodiment 1 same method, to make solid electrolytic capacitor to the 4-dioxin.
Embodiment 3
[use 2-propyl group-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-propyl group-EDOT)]
Prepare the capacitor element that is over embodiment 1 same polymerization pre-treatment, except using 2-propyl group-2,3-dihydro-thiophene also [3; 4-b]-1, (2-propyl group-EDOT) replaces the 2-methyl-2 of embodiment 1 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) as being used in beyond the polymeric compounds, all the other are to handle with embodiment 1 same method, to make solid electrolytic capacitor to the 4-dioxin.
Comparative example 1
[use 2, the 3-dihydro-thiophene is [3,4-b]-1 also, the manufacture method of the solid electrolytic capacitor of 4-dioxin (EDOT)]
Prepare the capacitor element that is over embodiment 1 same polymerization pre-treatment, except using 2,3-dihydro-thiophene also [3; 4-b]-1,4-dioxin (EDOT) replaces the 2-methyl-2 of embodiment 1,3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) as being used in beyond the polymeric compounds, all the other are to handle with embodiment 1 same method, to make solid electrolytic capacitor to the 4-dioxin.
The electrical characteristics of initial electrical characteristics, electric capacity impregnation rate, leakage current and the withstand voltage of the solid electrolytic capacitor that will obtain through each embodiment 1～3 and comparative example 1 are shown in table 1.
Table 1
As shown in table 1 learning, the result of compound more miscellaneous, the solid electrolytic capacitor ratio that obtains at embodiment 1～3 uses the solid electrolytic capacitor of the EDOT of comparative example also to have low equivalent series resistance.
Learn that particularly its ESR of solid electrolytic capacitor that obtains through embodiment 1 is lowered significantly.
Get 0.3g as 50% p-methyl benzenesulfonic acid iron/butanol solution of oxidant to 6ml vial (vial), with 20 ℃ of insulations 30 minutes.
Secondly, get 0.1g as the 2-methyl-2 that is used in polymeric compounds, the 3-dihydro-thiophene is [3,4-b]-1 also, 4-dioxin (2-methyl-EDOT), make an addition to vial and begin instrumentation.
Through after 5 seconds, stir 10 seconds of content in the vial tempestuously after adding with spatula (spatula).
Measure the time that finishes to stir till beginning to separate out to solid in vial afterwards.With its as a result induction-arrangement in table 2.
In addition, the polymerization speed in the table 2 is meant that the second number of being separated out by solid deducts 10 seconds value.
Under the situation of embodiment 4, except using 2-ethyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-ethyl-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1, (the 2-methyl-EDOT) in addition, all the other are to experimentize with the situation of embodiment 4 is just the same to the 4-dioxin.The result is shown in table 2.
Under the situation of embodiment 4, except using 2-propyl group-2,3-dihydro-thiophene also [3; 4-b]-1, (2-propyl group-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1, (the 2-methyl-EDOT) in addition, all the other are to experimentize with the situation of embodiment 4 is just the same to the 4-dioxin.The result is shown in table 2.
Comparative example 2
Under the situation of embodiment 4, except using 2-hexyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-hexyl-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1, (the 2-methyl-EDOT) in addition, all the other are to experimentize with the situation of embodiment 4 is just the same to the 4-dioxin.Polymerization speed can't be confirmed separating out of solid in measuring.The viscosity of content rises through time ground, and content becomes tar (tar) shape.The motionless time of liquid is shown in table 2.
Comparative example 3
Under the situation of embodiment 4, except using 2,3-dihydro-thiophene also [3; 4-b]-1,4-dioxin (EDOT) replaces 2-methyl-2,3-dihydro-thiophene also [3; 4-b]-1, (the 2-methyl-EDOT) in addition, all the other are to experimentize with the situation of embodiment 4 is just the same to the 4-dioxin.The result is shown in table 2.
Table 2
According to the result of embodiment 4～6 and comparative example 1～2, be transverse axis with the carbon number of substituent methyl, ethyl, propyl group and the hexyl of EDOT, polymerization speed (second) is shown in Fig. 1 for the figure of the longitudinal axis.
Learn that by Fig. 1 when the alkyl of carbon number more than 3 was replaced in EDOT, polymerization speed postponed widely.
Situation at embodiment 1; Under the condition of humidity 22%, make 2-methyl-2,3-dihydro-thiophene also [3; 4-b]-1; (amount of 2-methyl-EDOT) is 1.10g to the 4-dioxin, prepares 50% p-methyl benzenesulfonic acid iron/butanol solution as oxidant, and both weight rate was mixed into 1: 2.5 and stirred for 60 seconds.
Secondly; The capacitor element that is used in embodiment 1 impregnated in this solution after 120 seconds, in gloves work box (glove box), put into behind the airtight bottle through 30 minutes after, with 45 ℃ of heating 2 hours; By airtight bottle taking-up capacitor element and with 105 ℃ of heating 35 minutes; With 125 ℃ of heating 1 hour, carry out chemical oxidising polymerisation, make and gather 2-methyl-EDOT and be formed in the capacitor element.The result is shown in table 3.
Under the situation of embodiment 7, except using 2-ethyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-ethyl-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods, to make solid electrolytic capacitor to the 4-dioxin.The result is shown in table 3.
Under the situation of embodiment 7, except using 2-propyl group-2,3-dihydro-thiophene also [3; 4-b]-1, (2-propyl group-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods, to make solid electrolytic capacitor to the 4-dioxin.The result is shown in table 3.
Comparative example 4
Under the situation of embodiment 7, except using 2-hexyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-hexyl-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods, to make solid electrolytic capacitor to the 4-dioxin.The result is shown in table 3.
Comparative example 5
Under the situation of embodiment 7, except using 2,3-dihydro-thiophene also [3; 4-b]-2-methylol-1, (2-methylol-EDOT) replaces 2-methyl-2 to the 4-dioxin, 3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods, to make solid electrolytic capacitor to the 4-dioxin.The result is shown in table 3.
Comparative example 6
Under the situation of embodiment 7, except using 2-methyl-2,3-dihydro-thiophene also [3; 4-b]-1, (2-methyl-PDOT) replaces 2-methyl-2 to 4-dioxy heptane (dioxepine), 3-dihydro-thiophene also [3; 4-b]-1, (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods to the 4-dioxin; Attempt the making of solid electrolytic capacitor, but can't obtain the solid electrolytic capacitor of enough performances.
Comparative example 7
Under the situation of embodiment 7, except using 2,3-dihydro-thiophene also [3; 4-b]-1,4-dioxin (EDOT) replaces 2-methyl-2,3-dihydro-thiophene also [3; 4-b]-1; (the 2-methyl-EDOT) in addition, all the other are to handle with embodiment 7 same methods, to make solid electrolytic capacitor to the 4-dioxin.The result is shown in table 3.
Under 125 ℃ condition, the voltage that applies 4.0V is to the solid electrolytic capacitor that obtains through embodiment 7～9, comparative example 4～7 and implement heat resistant test.Before showing heat-resistant experiment, after 24 hours, after 48 hours and the result after 1000 hours in table 3.
According to the solid electrolytic capacitor that obtains through embodiment 7～9, comparative example 4,7, be transverse axis with the carbon number of substituent methyl, ethyl, propyl group and the hexyl of getting EDOT, ESR (m Ω) is shown in Fig. 2 for the figure of the longitudinal axis.
Learnt that by Fig. 2 when the alkyl of carbon number 1 or 2 was replaced in EDOT, ESR diminished, particularly when the alkyl of carbon number 1 was replaced in EDOT, ESR diminished.
Reference example
In 0.05 weight % phosphate aqueous solution, with 80 ℃, 25V anode being used size is 5 * 3 * 1mm
3Tantalum sintered object, anode line uses the anode bodies anodic oxidation 150 minutes of the about 100mg of weight of tantalum line, and is clean and carry out drying through the current of deionized water (deionized water), is used as capacitor element.In addition, the result who is used as capacitor to this state and measures the direct capacitance in the chemical liquids is 160 μ F.
[use 2-methyl-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-methyl-EDOT)]
Fig. 3 is the constructed profile in order to the structure of the explanation solid electrolytic capacitor relevant with embodiments of the invention 10.
Formation is the anode 11 of tantalum metal particle extrusion forming sintering, and this anode 11 of chemical treatment in the electrolyte of phosphate aqueous solution makes and makes dielectric oxide film 12 be formed at its surperficial capacitor element.
Secondly; The aforementioned capacitor element impregnated in by 2-methyl-2; The 3-dihydro-thiophene is [3,4-b]-1 also, and the 4-dioxin is (behind the chemical polymerization liquid that 2-methyl-EDOT), p-methyl benzenesulfonic acid iron (III), butanols are formed; In atmosphere, heat-treat, on dielectric oxide film 12, form by gathering the solid electrolyte 13 that 2-methyl-EDOT forms through chemical oxidising polymerisation.This dipping, heat treatment step are repeated to carry out more than 5 times.The heat treatment of this moment is after room temperature is placed 10 minutes, carries out 5 minutes with 150 ℃.
Then; On solid electrolyte 13, form graphite linings 14 and silver-colored paste (paste) layer 15 successively; See through conductivity solid 19 cathode wire 17 is connected in silver-colored paste layer 15; Positive wire 16 is connected in anode 11, and, accomplishes solid electrolytic capacitor through this class A of geometric unitA of package resin 18 molded (molding).
[use 2-ethyl-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-ethyl-EDOT)]
Prepare the capacitor element that is over embodiment 1 same polymerization pre-treatment, except monomer uses 2-ethyl-2,3-dihydro-thiophene also [3; 4-b]-1; (outside the 2-ethyl-EDOT), all the other are to handle with embodiment 10 same methods, to make solid electrolytic capacitor to the 4-dioxin.
[use 2-propyl group-2, the 3-dihydro-thiophene is [3,4-b]-1 also, the 4-dioxin (manufacture method of the solid electrolytic capacitor of 2-propyl group-EDOT)]
Prepare the capacitor element that is over embodiment 1 same polymerization pre-treatment, except monomer uses 2-propyl group-2,3-dihydro-thiophene also [3; 4-b]-1; (outside the 2-propyl group-EDOT), all the other are to handle with embodiment 10 same methods, to make solid electrolytic capacitor to the 4-dioxin.
Comparative example 8
[use 2, the 3-dihydro-thiophene is [3,4-b]-1 also, the manufacture method of the solid electrolytic capacitor of 4-dioxin (EDOT)]
Prepare the capacitor element that is over embodiment 9 same polymerization pre-treatments, except monomer is made into 2,3-dihydro-thiophene also [3; 4-b]-1; Outside the 4-dioxin (EDOT), all the other are to handle with embodiment 10 same methods, to make solid electrolytic capacitor.
The initial electrical characteristics of the solid electrolytic capacitor that will obtain through each embodiment 10～12 and comparative example 8, the electrical characteristics of electric capacity impregnation rate are shown in table 4.
Table 4
As shown in table 4 learning, the result of monomer more miscellaneous, solid electrolytic capacitor of the present invention (embodiment 10～12) compares with the solid electrolytic capacitor that uses known EDOT, has the high and low equivalent series resistance of electric capacity impregnation rate.
Claims (12)
1. a solid electrolytic capacitor is characterized in that,
Comprise so that the macromolecule that the compound polymerization through formula [1] expression obtains as solid electrolyte,
In this general formula [1], R
1Be the alkyl of the straight or branched of expression carbon number 1～6, Z is independent separately expression oxygen atom or sulphur atom.
2. a solid electrolytic capacitor is characterized in that,
Comprise so that the macromolecule that obtains through at least one polymerization in the compound of formula [2] and [3] expression as solid electrolyte,
3. solid electrolytic capacitor as claimed in claim 2 wherein, comprises so that the macromolecule that the compound polymerization of representing through this general formula [2] obtains as solid electrolyte.
4. solid electrolytic capacitor as claimed in claim 2, wherein, its porousness formed body that obtains with sintered valve effect metal particle is as anode,
And it comprises:
Be formed at the dielectric oxide film of this anode surface;
Comprise the high molecular solid electrolyte that at least one polymerization of compound that will be through this general formula [2] and [3] expression obtains in this dielectric oxide film surface; And
Comprise the carbon-coating that is formed at this high molecular surface and the negative electrode of silver layer.
5. solid electrolytic capacitor as claimed in claim 4 wherein, is used in this valve metals particulate of sintering and the valve metals particulate of the porousness formed body that obtains comprises at least one in tantalum metal particle and the niobium metal particulate,
The CV of per unit mass is long-pending to be shown more than the 20000 μ FV/g.
6. the manufacturing approach of a solid electrolytic capacitor is characterized in that,
Have the macromolecule that the compound polymerization through formula [1] expression will be obtained and be formed at the operation on the valve metals that is formed with dielectric oxide film,
In this general formula [1], R
1Be the alkyl of the straight or branched of expression carbon number 1～6, Z is independent separately expression oxygen atom or sulphur atom.
7. the manufacturing approach of a solid electrolytic capacitor is characterized in that,
Have the macromolecule that at least one polymerization that will make the compound through formula [2] and [3] expression obtains and be formed at the operation on the valve metals that is formed with dielectric oxide film,
8. like the manufacturing approach of claim 6 or 7 described solid electrolytic capacitors, wherein, the operation that this macromolecule is formed on the valve metals that is formed with dielectric oxide film comprises:
Make in liquid phase (A) be selected from by the group that forms through the compound of this general formula [1], [2] and [3] expression at least one, (B) alloy and (C) the oxidant operation that contacts and carry out polymerization.
9. the manufacturing approach of solid electrolytic capacitor as claimed in claim 8, wherein, should (B) alloy and (C) oxidant use and have (B) alloy and (C) both compound of character of oxidant.
10. the manufacturing approach of solid electrolytic capacitor as claimed in claim 9, wherein, have this (B) alloy and (C) both compound of character of oxidant be the organic sulfonic acid molysite,
This liquid phase comprises the organic sulfonic acid molysite with the scope of 40～70 weight %.
11. the manufacturing approach of solid electrolytic capacitor as claimed in claim 7, wherein, its porousness formed body that obtains with sintered valve effect metal particle is as anode,
And it comprises:
Form the operation of dielectric oxide film at this anode surface;
The macromolecule that at least one polymerization of compound through this general formula [2] and [3] expression will be obtained is formed at the operation on the anode that is formed with this dielectric oxide film; And
Form the operation of the negative electrode that comprises carbon-coating and silver layer on this high molecular surface.
12. the manufacturing approach of solid electrolytic capacitor as claimed in claim 11, wherein, the operation that this macromolecule is formed on the anode that is formed with this dielectric oxide film comprises:
Make in liquid phase (A) be selected from by at least one of the group that forms through the compound of this general formula [1], [2] and [3] expression and (C) oxidant contact and carry out the operation of chemical oxidising polymerisation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009252488A JP4925144B2 (en) | 2009-06-30 | 2009-11-02 | Manufacturing method of solid electrolytic capacitor |
| JP2009-252488 | 2009-11-02 | ||
| PCT/JP2010/006448 WO2011052237A1 (en) | 2009-11-02 | 2010-11-01 | Solid electrolytic capacitor and method for producing same |
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| CN (1) | CN102612722A (en) |
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| CN110444396A (en) * | 2018-05-02 | 2019-11-12 | 钰邦科技股份有限公司 | Wound capacitor component and its manufacturing method for lift structure intensity |
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| JP5788282B2 (en) | 2011-09-29 | 2015-09-30 | Ｎｅｃトーキン株式会社 | Solid electrolytic capacitor and manufacturing method thereof |
| US9362057B2 (en) | 2012-07-26 | 2016-06-07 | Industrial Technology Research Institute | Electrolyte mixture for electrolytic capacitor, composition for conductive polymer synthesis and conductive polymer solid electrolytic capacitor formed by using the same |
| KR101669574B1 (en) | 2013-10-10 | 2016-10-26 | 주식회사 엘지화학 | method for manufacturing a surface-treated transparent conductive high molecular thin film and transparent electrode manufactured by using the same |
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|---|---|---|---|---|
| US20030007318A1 (en) * | 2001-06-06 | 2003-01-09 | Matsushita Electric Industrial Co., Ltd. | Anode member for a solid electrolytic capacitor, an electrolytic capacitor using the same, and a method of making the same |
| JP2004189789A (en) * | 2002-12-09 | 2004-07-08 | Matsushita Electric Ind Co Ltd | Conductive polymer and solid electrolytic capacitor using the same |
| JP2005039276A (en) * | 2003-07-14 | 2005-02-10 | Hc Starck Gmbh | Polythiophene having alkylene oxythiathiofoehn unit in electrolytic capacitor |
-
2010
- 2010-10-29 TW TW099137122A patent/TW201131601A/en unknown
- 2010-11-01 KR KR1020127010205A patent/KR20120113701A/en not_active Application Discontinuation
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030007318A1 (en) * | 2001-06-06 | 2003-01-09 | Matsushita Electric Industrial Co., Ltd. | Anode member for a solid electrolytic capacitor, an electrolytic capacitor using the same, and a method of making the same |
| US6522527B2 (en) * | 2001-06-06 | 2003-02-18 | Matsushita Electric Industrial Co., Ltd. | Anode member for a solid electrolytic capacitor, an electrolytic capacitor using the same, and a method of making the same |
| JP2004189789A (en) * | 2002-12-09 | 2004-07-08 | Matsushita Electric Ind Co Ltd | Conductive polymer and solid electrolytic capacitor using the same |
| JP2005039276A (en) * | 2003-07-14 | 2005-02-10 | Hc Starck Gmbh | Polythiophene having alkylene oxythiathiofoehn unit in electrolytic capacitor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110444396A (en) * | 2018-05-02 | 2019-11-12 | 钰邦科技股份有限公司 | Wound capacitor component and its manufacturing method for lift structure intensity |
| CN110444396B (en) * | 2018-05-02 | 2022-02-11 | 钰邦科技股份有限公司 | Wound capacitor assembly for improving structural strength and method for manufacturing same |
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| KR20120113701A (en) | 2012-10-15 |
| TW201131601A (en) | 2011-09-16 |
| WO2011052237A1 (en) | 2011-05-05 |
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