CN114496578A - Method for producing electrolytic capacitor - Google Patents
Method for producing electrolytic capacitor Download PDFInfo
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- CN114496578A CN114496578A CN202011157978.0A CN202011157978A CN114496578A CN 114496578 A CN114496578 A CN 114496578A CN 202011157978 A CN202011157978 A CN 202011157978A CN 114496578 A CN114496578 A CN 114496578A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229920000123 polythiophene Polymers 0.000 claims abstract description 20
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 18
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 5
- 229920000547 conjugated polymer Polymers 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- -1 poly (p-phenylene-vinylene) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NBLHGCDPIWAGAS-UHFFFAOYSA-N 2-ethylthiolane-3,4-dione Chemical compound O=C1C(SCC1=O)CC NBLHGCDPIWAGAS-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- IOVFHLJNAMPRHI-UHFFFAOYSA-N 2-oxo-2-thiophen-3-ylacetaldehyde Chemical compound O=CC(=O)C=1C=CSC=1 IOVFHLJNAMPRHI-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
- H01G9/15—Solid electrolytic capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- 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
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The invention discloses a preparation method of an electrolyte capacitor, which comprises the following steps. A conductive polymer solution is applied to a porous body. The porous body includes a porous electrode body having an electrode material and a dielectric layer covering an outer surface of the electrode material. The conductive polymer solution comprises conductive polymer particles, the conductive polymer particles comprise at least one of polythiophene with at least one sulfonic group and polyselenophene with at least one sulfonic group, the average particle size of the conductive polymer particles is 0.5-50 nanometers, and the content of metal cations in the conductive polymer solution is less than 500 mg/kg. Then, forming a solid electrolyte completely or partially covering the surface of the dielectric layer; the conductive polymer particles form a film having a specific conductivity in the dry state of greater than 25 Siemens/cm.
Description
Technical Field
The invention relates to a preparation method of a capacitor, in particular to a preparation method of an electrolyte capacitor.
Background
A commercially available solid electrolyte capacitor generally includes: a porous metal electrode, an oxide layer on the surface of the porous metal electrode, a solid electrolyte incorporated within the porous structure of the porous metal electrode, an external electrode (linker) such as a silver layer, and electrical connectors and envelopes (encapsulation).
Examples of the solid electrolyte capacitor include capacitors made using a charge transfer composite or pyrolusite or polymer solid electrolyte with tantalum, aluminum, niobium and niobium oxides as materials. The advantage of using a porous body is that a high surface area can result in a higher capacitance density, that is, the characteristic of high capacitance can be achieved in a small space.
The pi-conjugated polymer is particularly suitable for use as a solid electrolyte because of its high conductivity. Pi-conjugated polymers are also known as conducting polymers or synthetic metals. Polymers are increasingly economically important because they are superior to metals in terms of processability, weight and properties that can be adjusted by chemical modification. Examples of known pi-conjugated polymers are: polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene and poly (p-phenylene-vinylene), of particular importance is polythiophene, of which the industrially used is poly-3, 4-dioxoethylthiophene, often also known as poly (3,4-ethylenedioxythiophene), and the oxidized form of which has very high electrical conductivity.
Technical developments in the electronics field have increasingly required solid electrolyte capacitors with very low Equivalent Series Resistance (ESR) due to reduced logic voltages, increased integration density and increased cycle frequency in integrated circuits. Moreover, a low ESR also reduces energy consumption, particularly for applications operating with mobile batteries. Therefore, it is desirable to reduce ESR of the solid electrolytic capacitor as much as possible.
The preparation of solid electrolytes from 3, 4-dioxoethylthiophene and the use of cationic polymers thereof prepared by oxidative polymerization as solid electrolytes in electrolytic capacitors are disclosed in the prior art. Poly (3, 4-dioxyethylthiophene) is used as a substitute for manganese dioxide or a charge transfer complex in a solid electrolyte capacitor, and is capable of reducing equivalent series resistance and improving frequency properties due to its higher conductivity.
In addition, poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), which is a complex of poly (3,4-ethylenedioxythiophene) and poly (p-styrenesulfonic acid), has been increasingly valued for its good electrical conductivity and low polymerization rate. However, PETDOT: PSS still has some problems to overcome.
For example, PEDOT: PSS is generally produced by in-situ polymerization (in-situ polymerization), using which PEDOT: the particle size of PSS is large, which allows PEDOT: PSS cannot effectively fill the interior of the porous metal body. Thus, when the capacitor is immersed in a solution containing PEDOT: in the case of a solution of PSS, the impregnation rate is generally poor.
And, PEDOT: PSS itself has the property of absorbing water, but capacitor components are sensitive to moisture once PEDOT: the PSS absorbs moisture from the environment, exposing the capacitor element to moisture, and the electrical characteristics of the capacitor element may be negatively affected, or even directly fail. Thus, when PEDOT is used: when the PSS is used as a solid electrolyte material, a package structure with better water resistance is required.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an electrolytic capacitor aiming at the defects of the prior art.
In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a method for manufacturing an electrolytic capacitor. The method for manufacturing the electrolytic capacitor includes the steps of: applying a conductive polymer solution on a porous body; wherein the porous body includes a porous electrode body having an electrode material and a dielectric layer covering an outer surface of the electrode material; the conductive polymer solution comprises conductive polymer particles, the content of metal cations in the conductive polymer solution is less than 500 mg/kg, the conductive polymer particles comprise polythiophene with at least one sulfonic group or polyselenophene with at least one sulfonic group, the average particle size of the conductive polymer particles in the conductive polymer solution is 0.5-50 nm, and the specific conductivity of a film obtained by the conductive polymer particles in a dry state is more than 25 siemens/cm. A solid electrolyte is formed that completely or partially covers the dielectric surface.
Preferably, the conductive polymer particles have a D90 particle size of less than 50 nanometers.
Preferably, the conductive polymer particles have a D10 particle size of greater than 0.5 nm.
Preferably, the content of the transition metal in the conductive polymer solution is less than 100 mg/kg.
Preferably, the content of iron metal in the conductive polymer solution is less than 100 mg/kg.
Preferably, the chemical structural formula of the polythiophene with at least one sulfonic acid group is shown as the formula (I), and the chemical structural formula of the polyselenophene with at least one sulfonic acid group is shown as the formula (II):
in the formula (I) and the formula (II), X and Y are each independently selected from the group consisting of an oxygen atom, a sulfur atom and-NR1A group of the formed; r1Is selected from the group consisting of hydrogen, alkyl groups having 1 to 24 carbon atoms, and aromatic groups; k is any integer between 1 and 50.
In the formula (I) and the formula (II), Z is- (CH)2)m-CR2R3-(CH2)n-；R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; r3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; m is an integer of 0 to 3, n is an integer of 0 to 3, p is an integer of 0 to 6, q is 0 or 1, r is an integer of 1 to 4, Ar is an arylene group; r4 is selected from hydrogen atomA substituted or unsubstituted alkyl group having 1 to 24 carbon atoms and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation.
Preferably, the chemical structural formula of the polythiophene with at least one sulfonic acid group is shown as formula (III) and formula (IV), and the chemical structural formula of the polyselenophene with at least one sulfonic acid group is shown as formula (V) and formula (VI):
in the formulae (III) to (VI), k is an arbitrary integer of 1 to 50, and Z is- (CH)2)m-CR2R3-(CH2)n-；R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; r3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the same; m is an integer of 0 to 3, n is an integer of 0 to 3, p is an integer of 0 to 6, q is 0 or 1, r is an integer of 1 to 4, Ar is an arylene group; r4Is selected fromIn the group consisting of hydrogen atom, substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation.
Preferably, in one embodiment of the present invention, the chemical structure of the polythiophene having at least one sulfonic acid group is represented by one of formulas (VII) to (XII), and the chemical structure of the polyselenophene having at least one sulfonic acid group is represented by one of formulas (XIII) to (XVIII):
preferably, in formulae (VII) to (XVIII), k is any integer between 1 and 50, Ar is an arylene group; r4 is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl of 1 to 24 carbon atoms, and substituted or unsubstituted aryl of 4 to 16 carbon atoms; m + is a metal cation; p is an integer of 0 to 6, q is 0 or 1, and r is an integer of 1 to 4.
Preferably, the conductive polymer solution has an acid-base number of 3 to 8.
Preferably, the conductive polymer solution is at 20 deg.C for 100s-1The viscosity measured under the conditions of (1) is from 1 mPas to 160 mPas.
Preferably, the valve metal or the compound having electrical properties of the valve metal is an alloy of at least one metal element of tantalum, aluminum, titanium, zirconium, hafnium, vanadium, niobium with other elements or an alloy or compound of aluminum oxide or aluminum oxide with other elements.
Preferably, the dielectric is selected from the group consisting of: aluminum oxide, tantalum oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, barium titanate, barium oxide, and silicon oxide.
Preferably, the steps of applying the conductive polymer solution and curing the conductive polymer solution are repeated at least once.
Preferably, the metal of the metal oxide in the metal electrode and the dielectric layer is a different metal.
Preferably, the coverage of the dielectric layer with the solid electrolyte is greater than 80%.
Preferably, the solid electrolyte does not dissolve in water and swells by absorbing water.
One of the advantages of the present invention is that the method for preparing the electrolyte capacitor provided by the present invention can improve the characteristics of the electrolyte capacitor by using the technical characteristics of "polythiophene having at least one sulfonic acid group or polyselenophene having at least one sulfonic acid group" and "the average particle size of the conductive polymer particles is 0.5nm to 50 nm".
For a better understanding of the features and technical content of the present invention, reference should be made to the following detailed description of the invention and accompanying drawings, which are provided for purposes of illustration and description only and are not intended to limit the invention.
Drawings
Fig. 1 is a flow chart showing the steps of a method for producing an electrolytic capacitor according to the present invention.
FIG. 2 is a schematic sectional side view of an electrolytic capacitor according to the present invention.
Fig. 3 is a schematic side sectional view of a capacitor package structure according to the present invention.
Detailed Description
The following is a description of embodiments of the "method for producing an electrolytic capacitor" disclosed in the present invention by specific examples.
It is an object of the present invention to provide the above method and a capacitor improved by the method, which can satisfy these requirements if a solid electrolyte in the capacitor is prepared as a conductive polymer solution containing conductive polymer particles having an average particle diameter of 0.5 nanometers (nm) to 50nm and a specific conductivity of more than 25 siemens per centimeter (S/cm).
Accordingly, referring to fig. 1, the present invention provides a method for manufacturing an electrolytic capacitor, the method comprising the following steps. In step S1, a conductive polymer solution (a) is applied on a porous body including at least a porous electrode body as an electrode material and a dielectric covering a surface of the electrode material, the conductive polymer solution (a) containing at least conductive polymer particles (B). In step S2, a solid electrolyte is formed that completely or partially covers the dielectric surface; the average particle diameter of the conductive polymer particles (B) in the conductive polymer solution (A) is 0.5nm to 50nm, and the specific conductivity of a film prepared from the conductive polymer particles (B) is more than 25S/cm. The specific conductivity of the film obtained from the conductive polymer particles (B) is the specific conductivity of the film in a dry state.
The conductive polymer particles (B) must be less than 50nm to penetrate into the porous electrode body. The pore diameter of the porous electrode body is larger than 500nm, that is, the pore diameter of the porous electrode body is 10 times or more as large as that of the conductive polymer particles (B). The conductive polymer particles (B) form a thin film having sufficient conductivity in the electrode body because the resistance is controlled by the contact resistance between particles, and generally increases as the particle diameter of the particles decreases.
The particle diameter of the conductive polymer particles (B) is measured by a transmission electron microscope.
In the method, the average particle diameter of the conductive polymer particles (B) in the conductive polymer solution (A) is preferably about 1nm to 80nm, particularly preferably 1nm to 50nm, more preferably 1nm to 25 nm.
In the method, the value of D90 in the particle size distribution of the conductive polymer particles (B) in the conductive polymer solution (A) is preferably less than 50nm, particularly preferably less than 40nm, more preferably less than 30nm, and most preferably less than 25 nm.
In the method, the value of D10 in the particle size distribution of the conductive polymer particles (B) in the conductive polymer solution (A) is preferably more than 0.5nm, particularly preferably more than 1nm, and more preferably more than 3 nm.
In the present specification, the D10 value of the particle size distribution means that 10% by weight of the entire weight of the conductive polymer particles (B) in the conductive polymer solution (a) are those conductive polymer particles (B) having a particle size of D10 or less. The D90 value of the particle size distribution means that 90% by weight of the entire weight of the conductive polymer particles (B) in the conductive polymer solution (A) are those particles (B) having a particle size of D90 or less.
It is preferred to use a conductive polymer solution (A) having a specific conductivity of more than 25S/cm, particularly preferably more than 50S/cm, more preferably more than 100S/cm, most preferably more than 500S/cm, and in a particularly preferred embodiment more than 1000S/cm after forming a dry film.
In the method, the content of the metal cation in the electroconductive polymer solution (a) is preferably less than 500 mg/kg (mg/kg), particularly preferably less than 100mg/kg, and more preferably less than 20 mg/kg.
In the method, the content of the transition metal in the electroconductive polymer solution (A) is preferably less than 100mg/kg, particularly preferably less than 10mg/kg, and more preferably less than 2 mg/kg.
In the method, the content of iron in the electroconductive polymer solution (A) is preferably less than 100mg/kg, particularly preferably less than 10mg/kg, and more preferably less than 5 mg/kg.
The low concentration of metal in the conductive polymer solution has the great advantage that the dielectric is not damaged during the formation of the solid electrolyte and during the subsequent operation of the capacitor.
In the electrolytic capacitor produced by the method of the present invention, the electrode material forms a porous body having a high surface area, for example, in the form of a porous sintered body or a roughened thin film. This porous body is also referred to hereinafter simply as an electrode body.
The dielectric-coated electrode body is also referred to hereinafter simply as an oxidized electrode body. The term "oxidized electrode body" also includes electrode bodies that cover dielectrics that are not prepared by oxidation of the electrode body.
The electrode body covered with the dielectric and completely or partially covered with the solid electrolyte is hereinafter also simply referred to as a capacitor main body.
The outer surface of the capacitor body is understood to be the outer surface of the capacitor body.
In the context of the present invention, the term "polymer" includes all compounds having more than one identical or different repeating unit.
Conductive polymers are to be understood here in particular as compounds of the class of pi-conjugated polymers which, after oxidation or reduction, are electrically conductive. Preferably, the electrically conductive polymer is understood to be a pi-conjugated polymer having a specific conductivity after oxidation of at least the order of 1. mu.S/cm.
The conductive polymer particles (B) in the conductive polymer solution (a) are preferably polythiophene (polythiophene) having at least one sulfonic acid group (sulfophenyl hydroxide), as shown in formula (I), or polyselenophene (selenophene) having at least one sulfonic acid group (sulfophenyl hydroxide), as shown in formula (II). Or, the polythiophene also comprises polythiophene with at least one sulfonic group shown in the formula (I) and polyselenophene with at least one sulfonic group shown in the formula (II).
In the formula (I) and the formula (II), k is any integer between 1 and 50, and X and Y are independently selected from oxygen atom, sulfur atom and-NR1The group formed. R1Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms.
The "alkyl group having 1 to 24 carbon atoms" may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1, 1-dimethylpropyl group, a 1, 2-dimethylpropyl group, a 2, 2-dimethylpropyl group, a n-hexyl group, a n-heptyl group or a n-octyl group; preferably, R1Is an alkyl group having 1 to 4 carbon atoms.
In the formula (I) and the formula (II), Z is- (CH)2)m-CR2R3-(CH2)n-, where m is an integer of 0 to 3 and n is an integer of 0 to 3. In the description of the present invention, "m is an integer of 0 to 3" means that m may be 0, 1,2 or 3; "- (CH)2) - "represents a methylene group (methylene). In other words, the carbon number or chain length of the substituent Z may vary depending on the values of m and n. For example, when m and n are both 0, the substituent Z is "-CR2R3X, Z, Y in formula (I) and carbons No. 3 and 4 in the thiophene ring structure form a five-ring structure. When the sum of m and n is 1, the substituent Z is "- (CH)2)-CR2R3X, Z, Y in formula (I) and carbons No. 3 and 4 in the thiophene ring structure form a six-ring structure (as shown in formulas (VII) to (XII)). Similarly, X, Z, Y in formula (II) and carbons 3 and 4 in the selenophene ring structure form a six-ring structure (as shown in formulas (XIII) to (XVIII)).
In the substituent Z, R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rThe group formed. R3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rThe group formed. And, in R2And R3Wherein each p is independently an integer of 0 to 6; q is each independently 0 or 1; each r is independently an integer from 1 to 4; ar is arylene (arylene); r4Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation. In one embodiment, M+Lithium ion, sodium ion, potassium ion or ammonium ion.
In view of the above, the conductive polymer of formula (I) of the present invention does not include poly (3,4-ethylenedioxythiophene) (PEDOT). That is, the present invention uses a conductive polymer different from the conductive polymer used in the industry, and still has excellent electrical characteristics.
In a preferred embodiment, X and Y in formula (I) and formula (II) are oxygen atoms, the polythiophene having at least one sulfonic acid group is represented by formula (III), and the polyselenophene having at least one sulfonic acid group is represented by formula (V). In another preferred embodiment, one of X and Y in the formula (I) and the formula (II) is an oxygen atom and the other is a sulfur atom, the polythiophene having at least one sulfonic acid group is represented by the following formula (IV), and the polyselenophene having at least one sulfonic acid group is represented by the following formula (VI).
In the formulae (III) to (VI), k is an arbitrary integer between 1 and 50, and the substituent Z is- (CH)2)m-CR2R3-(CH2)n-, where m is an integer of 0 to 3 and n is an integer of 0 to 3. In the substituent Z, R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rThe group formed. R3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rThe group formed. At R2And R3Wherein p is each independently an integer of 0 to 6, q is each independently 0 or 1, R is each independently an integer of 1 to 4, Ar is an arylene group, R is an aromatic group4Is selected from the group consisting of substituted by hydrogen atomsOr an unsubstituted alkyl group having 1 to 24 carbon atoms and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms, M+Is a metal cation. In one embodiment, M+Lithium ion, sodium ion, potassium ion or ammonium ion.
In a preferred embodiment, X and Y are both oxygen atoms and the sum of m and n is 1, the polythiophene having at least one sulfonic acid group may be represented by one of the following formulas (VII) to (XII), and the polyselenophene having at least one sulfonic acid group may be represented by one of the following formulas (XIII) to (XVIII):
in the formulae (VII) to (XVIII), k is any integer between 1 and 50,
represents methylene (methylene) with the aforementioned "- (CH)2) - "same, for the sake of brevity is indicated only by carbon-carbon bonds. In the formulae (VII) to (XVIII), p is each independently an integer of 0 to 6, q is each independently 0 or 1, R is each independently an integer of 1 to 4, Ar is an arylene group, R is4Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation. In one embodiment, M+Lithium ion, sodium ion, potassium ion or ammonium ion.
In order to prevent the conductive polymer solution (a) from corroding the dielectric layer of the porous body, the ph of the conductive polymer solution (a) may be controlled by adding acid or alkali. In this embodiment, the pH of the conductive polymer solution is 1 to 14; preferably, the pH value of the conductive polymer solution is 1 to 8; more preferably, the pH of the conductive polymer solution is 3 to 8. The added acid or base does not deteriorate the film-forming property of the electroconductive polymer solution and does not volatilize even at a high temperature (for example, soldering temperature), and therefore, it is finally present in the solid electrolyte. For example, the base that can be added can be 2-dimethylaminoethanol, 2 '-iminodiethanol, or 2, 2', 2 "-nitrilotriethanol, and the acid that can be added can be polystyrene sulfonic acid. However, the above description is for illustrative purposes only and does not limit the present invention.
The viscosity of the electroconductive polymer solution (A) is 0.1 to 200 mPas (measured at 20 ℃ C., shear rate 100 s)-1) Depending on the application method. Preferably, the viscosity of the polymer solution (A) is 1 to 160 mPas. Preferably, the viscosity is from 1 to 20 mPas, particularly preferably from 1 to 10 mPas, more preferably from 3 to 5 mPas.
Please refer to fig. 2 and fig. 3. Fig. 2 is a schematic side sectional view of a capacitor of the present invention, and fig. 3 is a schematic structural view of a capacitor package structure according to an embodiment of the present invention. Specifically, the polymer composite material provided by the present invention can be applied to the solid electrolyte 102 of the cathode portion of the capacitor cell 10. In fig. 3, the capacitor unit 10 is the capacitor unit 10 in the stacked solid electrolytic capacitor package structure 1.
For example, as shown in fig. 2, the capacitor unit 10 may include a valve metal foil 100, a dielectric layer 101 covering the valve metal foil 100, a solid electrolyte 102 covering a portion of the dielectric layer 101, a carbon glue layer 103 covering the solid electrolyte 102, and a silver glue layer 104 covering the carbon glue layer 103. The structure of the capacitor unit 10 can be adjusted according to the actual requirements of the product. The solid electrolyte 102 is mainly used as a solid electrolyte of the capacitor cell 10.
As shown in fig. 3, the stacked solid electrolytic capacitor 1 includes a plurality of capacitor cells 10 stacked in sequence. In addition, the stacked type solid electrolytic capacitor 1 includes a conductive support 11. The conductive holder 11 includes a first conductive terminal 111 and a second conductive terminal 112 separated from the first conductive terminal 111 by a predetermined distance. In addition, the plurality of capacitor units 10 stacked in sequence and electrically connected to each other have a first positive electrode portion P electrically connected to the first conductive terminal 111 of the corresponding conductive support 11 and a first negative electrode portion N electrically connected to the second conductive terminal 112 of the corresponding conductive support 11. In addition, a plurality of capacitor units 10 stacked in sequence and electrically connected to each other may be encapsulated by the encapsulant 12, thereby forming the stacked solid electrolytic capacitor 1.
[ advantageous effects of the embodiments ]
One of the advantages of the present invention is that the method for manufacturing the electrolyte capacitor provided by the present invention can improve the characteristics of the electrolyte capacitor by using the technical characteristics of at least one of polythiophene having at least one sulfonic acid group and polyselenophene having at least one sulfonic acid group and conductive polymer particles having an average particle size of 0.5nm to 50 nm.
More specifically, the present invention provides a method for preparing an electrolytic capacitor, which can make the formed solid electrolyte have good specific conductivity by the technical characteristics of "the D90 particle size of the conductive polymer particles is less than 150 nm" and "the D10 particle size of the conductive polymer particles is greater than 1 nm".
More specifically, the present invention provides a method for manufacturing an electrolytic capacitor, which is capable of facilitating the application of a conductive polymer solution to a porous body by the technical feature that "the viscosity of the conductive polymer solution is 1 to 20mPa · s".
The disclosure is only a preferred embodiment of the invention, and is not intended to limit the scope of the claims, so that all technical equivalents and modifications using the contents of the specification and drawings are included in the scope of the claims.
Claims (13)
1. A method for producing an electrolytic capacitor, characterized in that the method for producing an electrolytic capacitor comprises:
applying a conductive polymer solution on a porous body; wherein the porous body comprises a porous electrode body having an electrode material and a dielectric layer covering an outer surface of the electrode material; the conductive polymer solution comprises conductive polymer particles; and
forming a solid electrolyte completely or partially covering the surface of the dielectric layer;
wherein the conductive polymer particles comprise at least one of polythiophene with at least one sulfonic group and polyselenophene with at least one sulfonic group, the average particle diameter of the conductive polymer particles in the conductive polymer solution is 0.5-50 nm, the specific conductivity of a film formed by the conductive polymer particles in a dry state is more than 25 Siemens/cm, and the content of metal cations in the conductive polymer solution is less than 500 mg/kg.
2. The method of manufacturing an electrolytic capacitor as recited in claim 1, wherein the conductive polymer particles have a D90 particle size of less than 50 nm.
3. The method of manufacturing an electrolytic capacitor as recited in claim 1, wherein the conductive polymer particles have a D10 particle size of more than 0.5 nm.
4. The method of producing an electrolytic capacitor as claimed in claim 1, wherein the content of the transition metal in the electroconductive polymer solution is less than 100 mg/kg.
5. The method of manufacturing an electrolytic capacitor as recited in claim 1, wherein the content of iron metal in the conductive polymer solution is less than 100 mg/kg.
6. The method for producing an electrolyte capacitor as claimed in claim 1, wherein the polythiophene having at least one sulfonic acid group has a chemical formula shown in formula (I), and the polyselenophene having at least one sulfonic acid group has a chemical formula shown in formula (II):
wherein X and Y are each independently selected from the group consisting of an oxygen atom, a sulfur atom and-NR1A group of the formed; r1Is selected from the group consisting of hydrogen, alkyl groups having 1 to 24 carbon atoms, and aromatic groups; k is any integer between 1 and 50;
wherein Z is- (CH)2)m-CR2R3-(CH2)n-；R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the same; r3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; m is an integer of 0 to 3, n is an integer of 0 to 3, p is an integer of 0 to 6, q is 0 or 1, r is an integer of 1 to 4, Ar is an arylene group; r4Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation.
7. The method for producing an electrolyte capacitor as claimed in claim 1, wherein the polythiophene having at least one sulfonic acid group has a chemical structure represented by the formulae (III) and (IV), and the polyselenophene having at least one sulfonic acid group has a chemical structure represented by the formulae (V) and (VI):
wherein k is an integer of 1 to 50, and Z is- (CH)2)m-CR2R3-(CH2)n-；R2Is selected from the group consisting of hydrogen atom, - (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; r3Is selected from the group consisting of- (CH)2)p-O-(CH2)q-SO3 -M+、-(CH2)p-NR4[(CH2)q-SO3 -M+]、-(CH2)p-NR4[Ar-SO3 -M+]And- (CH)2)p-O-Ar-[(CH2)q-SO3 -M+]rA group of the formed; m is an integer of 0 to 3, n is an integer of 0 to 3, p is an integer of 0 to 6, q is 0 or 1, r is an integer of 1 to 4, Ar is an arylene group; r4Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation.
8. The method for producing an electrolyte capacitor as claimed in claim 1, wherein the polythiophene having at least one sulfonic acid group has a chemical formula represented by one of formulae (VII) to (XII), and the polyselenophene having at least one sulfonic acid group has a chemical formula represented by one of formulae (XIII) to (XVIII):
wherein k is any integer between 1 and 50, and Ar is arylene; r4Is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 16 carbon atoms; m+Is a metal cation; p is an integer of 0 to 6, q is 0 or 1, and r is an integer of 1 to 4.
9. The method of manufacturing an electrolytic capacitor as claimed in claim 1, wherein the conductive polymer solution has an acid-base number of 3 to 8.
10. The method for producing an electrolytic capacitor as claimed in claim 1, wherein the electroconductive polymer solution is used at 20 ℃ for 100 seconds-1The viscosity measured under the conditions of (1) is from 1 mPas to 160 mPas.
11. The method of manufacturing an electrolytic capacitor as claimed in claim 1, wherein the steps of applying the electroconductive polymer solution and partially curing the electroconductive polymer solution are repeated at least once.
12. The method of manufacturing an electrolytic capacitor as recited in claim 1, wherein a coverage of the solid electrolyte on the dielectric layer is greater than 80% of the solid electrolyte.
13. The method of producing an electrolytic capacitor as recited in claim 1, wherein the solid electrolyte is insoluble in water and does not swell by absorbing water.
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| CN101263568A (en) * | 2005-09-13 | 2008-09-10 | H.C.施塔克有限公司 | Method for producing electrolyte capacitors |
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| CN104470966A (en) * | 2012-05-29 | 2015-03-25 | 索尔维美国有限公司 | Conductive polymer for solid electrolytic capacitor |
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