CN107017087B - 电容结构 - Google Patents
电容结构 Download PDFInfo
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- CN107017087B CN107017087B CN201611126816.4A CN201611126816A CN107017087B CN 107017087 B CN107017087 B CN 107017087B CN 201611126816 A CN201611126816 A CN 201611126816A CN 107017087 B CN107017087 B CN 107017087B
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- 239000003990 capacitor Substances 0.000 title abstract description 72
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 27
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 23
- 239000007787 solid Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000011241 protective layer Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- CWPOINBYXIYTHX-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO CWPOINBYXIYTHX-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- -1 polyethylene pyrrole Pyrrolidone Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- LWLURCPMVVCCCR-UHFFFAOYSA-N iron;4-methylbenzenesulfonic acid Chemical compound [Fe].CC1=CC=C(S(O)(=O)=O)C=C1 LWLURCPMVVCCCR-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- XYIFTULRAWWQDU-UHFFFAOYSA-N benzenesulfonic acid;iron Chemical compound [Fe].OS(=O)(=O)C1=CC=CC=C1 XYIFTULRAWWQDU-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229940009626 etidronate Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 229960003019 loprazolam Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/02—Diaphragms; Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/055—Etched foil electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/07—Dielectric layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
本发明提供的电容结构,包括:正极;介电层,位于正极上;以及有机‑无机复合物层,位于介电层上;负极;以及导电性共轭高分子电解质,位于有机‑无机复合物层与负极之间。
Description
技术领域
本发明涉及电容器结构,尤其涉及其有机-无机复合物层的组成。
背景技术
长期以来,电解电容器发展的一项主要课题即为提高电解质的导电度,以降低电容器的等效串联电阻,达到高频低阻抗并具高可靠度的特性。由于导电性高分子较传统电解电容器所用的液态电解液或是固态有机半导体错盐,如TCNQ复合盐,具有更高的导电度,且具有适度的高温绝缘化特性,因此导电性高分子成为现今电解电容器所使用的固态电解质的开发潮流。
虽然相较于传统液态电解质,以原位聚合法所合成的导电性共轭高分子作为电解质的电容器具有低阻抗与热稳定佳等优点,但是导电性共轭高分子耐电压特性远不如液态电解质。因此低工作电压成为导电性共轭高分子在电解电容用途上的最大阻碍。
综上所述,目前亟需新的电容结构克服上述问题。
发明内容
本发明一实施例提供的电容结构,包括:正极;介电层,位于正极上;以及有机-无机复合物层,位于介电层上;负极;以及导电性共轭高分子电解质,位于有机-无机复合物层与负极之间。
附图说明
图1为依据本发明一实施例的电容结构的示意图。
<附图标记说明>
10 电容结构;
11A 正极;
11B 介电层;
11C 有机-无机复合物层;
13 电解质;
15 负极。
具体实施方式
如图1所示的实施例中,电容结构10包括正极11A、正极11A上的介电层11B、介电层11B上的有机-无机复合物层11C、负极15、与夹设于有机-无机复合物层11C与负极15之间的电解质13。在一实施例中,正极11A所使用的阀金属包括铝、钽、铌、钛、锆、或上述的合金。正极11A的形状可为片状箔或以颗粒烧结成多孔锭状。依据需求可进行刻蚀以获取更大比表面积。
在一实施例中,介电层11B可为上述正极11A的氧化物。举例来说,可采用化学方式处理正极11A的表面,以形成介电层11B于正极11A的表面上。在其他实施例中,可采用其他方式形成介电层11B,比如溅射金属氧化物于正极11A上。
上述有机-无机复合物层11C可为单层或多层结构的复合层。在一实施例中,有机-无机复合物层11C系由绝缘高分子与无机物混合而成。举例来说,可先将绝缘高分子的单体或前驱物与无机物混合后,再聚合成绝缘高分子。此外,亦可先将绝缘高分子的单体或前驱物聚合成绝缘高分子后,再与无机物混合。
在一实施例中,有机-无机复合物层11C的绝缘高分子可为含氮高分子如聚乙烯吡咯烷酮[poly(vinyl pyrrolidone),PVP)];含氧高分子如聚氧化乙烯[(poly(ethyleneoxide),PEO)];或上述的混掺物。
上述有机-无机复合物层的绝缘高分子其分子量并无特别限制,但线性绝缘高分子的数目平均分子量可介于1000至2000000之间。分子量过低,则线性高分子室温下呈现液态,不易于介电层表面形成稳定的层状结构。分子量过高,则影响有机-无机复合物层在介电层表面成膜。
上述无机物可先以前驱物的形式先与绝缘高分子或绝缘高分子前驱物混合后,再反应形成无机物。此外,也可先将无机物的前驱物反应形成无机物后,再与绝缘高分子或绝缘高分子前驱物混合。
在一实施例中,无机物可为氧化铝、氧化锌、硼酸与氧化锌的组合、或硼酸与氢氧化铝的组合。在一实施例中,无机物为颗粒态,且平均粒径可小于或等于1000微米以良好分散于有机-无机复合物层11C中。在一实施例中,无机物的平均粒径介于10nm至100nm之间。上述有机-无机复合物层11C的绝缘高分子与无机物的重量比例可介于1:100至100:1之间,比如100:40。换句话说,上述有机-无机复合物层11C可包含1重量份的绝缘高分子与100至0.01重量份的无机物。
上述负极15可为金属箔片,并可依据需求可在金属箔片表面进行刻蚀以获得更大表面积,或是附着其他物质如碳或钛以提升化学稳定性或提高电容量。在一实施例中,负极15亦可为附着于电解质13上的导电银胶或碳胶。
上述电解质13可为导电性共轭高分子,比如掺杂态的聚噻吩、聚吡咯、或聚苯胺、或其衍生物。在一实施例中,导电性共轭高分子可为聚(3,4-乙烯二氧噻吩)(poly(3,4-ethylenedioxythiophene),PEDOT)、或含有上述结构的共聚合物或混掺物。
为使共轭高分子具有优良的导电度,共轭高分子以掺杂态为最佳。掺杂剂可为磺酸类化合物,如甲烷磺酸、苯磺酸、或对甲苯磺酸;磺酸类高分子如聚苯乙烯磺酸(poly(styrene sulfonic acid),PSS)或其共聚物;羧酸类化合物如苯甲酸、苯二甲酸、或琥珀酸(succinic acid);羧酸类高分子如聚丙烯酸或其共聚合物;胺基酸如甘胺酸;磷酸类化合物如磷酸、依替磷酸(Etidronic acid)、或磷酸二苯酯;或上述的组合。
上述共轭高分子的掺杂方式可为先聚合成共轭高分子后再添加掺杂剂进行掺杂、在共轭高分子聚合过程中即添加掺杂剂,或以氧化剂引发共轭高分子聚合时所产生的副产物作为掺杂剂进行掺杂,比如对甲苯磺酸铁引发共轭高分子聚合时所产生的对甲苯磺酸作为掺杂剂。
上述导电性共轭高分子合成方式可为原位(in-situ)化学聚合法,即取导电性共轭高分子的前驱物于有机-无机复合层11C的表面聚合;电化学聚合法,使导电性共轭高分子单体在有机-无机复合层11C的表面进行电化学聚合;将已合成完毕的水溶性导电高分子如PEDOT:PSS水溶液涂布或含浸于有机-无机复合层11C表面作为导电性共轭高分子。上述原位化学聚合法所使用的氧化剂可为含铁离子的盐类或含铜离子的盐类。上述含铁离子的盐类包括苯磺酸铁、对甲苯磺酸铁、氯化铁、硝酸铁、硫酸铁、或其组合。上述含铜离子的盐类包括过硫酸铜。
在一实施例中,可电化学腐蚀铝箔以形成高表面积的铝箔,并于其上附着碳层作为负极15。接着可视情况在正极11A与负极15之间夹设隔离纸(未图示),再卷绕成固态电解电容器素子(element)。在某些实施例中,可采用有机酸水溶液处理上述固态电解电容器素子,以修补破损的介电层11B。在一实施例中,有机酸可为草酸或醋酸。
接着将上述固态电解电容器素子含浸有机-无机复合物的水液中,再加热除水以形成有机-无机复合物层11C于介电层11B上。在一实施例中,绝缘高分子可为含氮或含氧聚合物,如聚乙烯吡咯烷酮(PVP)、聚氧化乙烯,其数目平均分子量介于1000至2000000之间。在一实施例中,无机物可为氧化铝、或氧化锌。在一实施例中,无机物为氧化铝。在一实施例中,无机物为氧化锌。在一实施例中,无机物为硼酸与氧化锌的组合。在一实施例中,无机物为硼酸与氢氧化铝的组合。
接着将上述固态电解电容器素子含浸于导电性共轭高分子的前驱物中,再聚合前驱物以形成导电性共轭高分子作为电解质13于正极11A与负极15之间。在一实施例中,导电性共轭高分子可为掺杂的聚噻吩、聚吡咯、聚苯胺、或聚(3,4-乙烯二氧噻吩)。
对固态电容结构而言,由于介电层的缺陷或厚度不均匀,局部介电层的耐电压特性较差。理想情况下,可藉由导电性共轭高分子电解质的局部绝缘反应提高局部介电层的耐电压特性。然而当电压过高或是介电层有严重缺陷时,可能会使导电性共轭高分子电解质发生大量绝缘,使电容器的电容量大幅衰退、阻抗升高、与漏电流过大,严重者甚至会因无法抵抗工作电压而发生短路。上述有机-无机复合物层可填补局部介电层(厚度较薄的部份)与结构缺陷,以提高电容器的耐电压并减少导电性共轭高分子电解质发生绝缘的机会。如此一来,电容器的阻抗与电容量将可长时间维持稳定。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举数个实施例作详细说明如下:
实施例
比较例1
以21V电化学电解反应处理正极铝箔,形成氧化铝介电层于正极铝箔上。以电化学腐蚀负极碳箔,形成高表面积的负极碳箔。在正极与负极之间夹设隔离纸,再卷绕成固态电解电容器素子(element)。以有机酸水溶液处理上述固态电解电容器素子,以修补破损氧化铝介电层。
接着将上述固态电解电容器素子含浸于3,4-乙烯二氧噻吩(EDOT)单体及浓度50wt%的甲苯磺酸铁乙醇溶液所组成的混合物中,加热混合物以加速聚合反应。在聚合反应时,最高温可达170℃以确保反应完全。经上述聚合反应后,形成导电性共轭高分子如掺杂的PEDOT于正极与负极之间。接着将此固态电解电容器素子套入铝壳,以橡胶盖封口,完成固态电解电容器制作并进行固态电解电容器的特性测试。最后在125℃下对电容器通以16V电流12小时,进行过电压负载测试,其电性如表2所列。
比较例2
与比较例1类似,差别在于将固态电解电容器素子含浸于3,4-乙烯二氧噻吩(EDOT)单体及浓度50wt%的甲苯磺酸铁乙醇溶液所组成的混合物中之前,先将固态电解电容器素子含浸于PVP(数目平均分子量为约1300000)的水液(见表1)中。之后加热至60℃后维持一小时,再加热至125℃后维持一小时以除水,即形成PVP层于氧化铝介电层上。之后形成掺杂的PEDOT、封口、特性测试、与过电压负载测试等步骤,均与比较例1类似。此实施例的电容器的电性如表2所列。
实施例1
与比较例1类似,差别在于将固态电解电容器素子含浸于3,4-乙烯二氧噻吩(EDOT)单体及浓度50wt%的甲苯磺酸铁乙醇溶液所组成的混合物中之前,先将固态电解电容器素子含浸于PVP(数目平均分子量为约1300000)与γ-Al2O3(粒径介于40nm-80nm之间)的水液(见表1)中。之后加热至60℃后维持一小时,再加热至125℃后维持一小时以除水,即形成PVP-γ-Al2O3的有机-无机复合物层于氧化铝介电层上。之后形成掺杂的PEDOT、封口、特性测试、与过电压负载测试等步骤,均与比较例1类似。此实施例的电容器的电性如表2所列。
实施例2
与实施例1类似,差别在于将PVP与γ-Al2O3的水液,置换为PVP与ZnO(粒径为约20nm)的水液(见表1),以形成PVP-ZnO的有机-无机复合物层于氧化铝介电层上。此实施例的电容器的电性如表2所列。
比较例3
与实施例1类似,差别在于将PVP与γ-Al2O3的水液,置换为PVP与TiO2(粒径小于25nm)的水液(见表1),以形成PVP-TiO2的有机-无机复合物层于氧化铝介电层上。此比较例的电容器的电性如表2所列。
表1
表2
*过电压负载测试后的电容器特性已扣除测试过程中发生短路的电容器。
如表2所示,电容器封口后,除了比较例1的100kHz ESR比较高之外,其余各比较例与实施例的电容量与100kHz ESR的特性相近。
实施例1与2与比较例1至3所采用的21V电化学电解反应所形成的氧化铝介电层在未经有机无机保护层处理之前的适合最高工作电压为10V。经过12小时,125℃高温的16V过电压负载测试后,不同电容器特性表现出极大的差异。比较例1的电容器(介电层直接接触导电性共轭高分子电解质)的静电容量衰退17.51%,且100kHz ESR亦大幅上升,16V平均漏电流亦高达1743μA,且电容短路率高达60%。比较例2的电容器(具有PVP层位于介电层上)在过电压负载测试之后,其电容量衰退8.69%,100kHz ESR由封口后的14.43mΩ上升至18.18mΩ,增加约26%。至于具有有机-无机复合物层于介电层上的固态电容中,实施例1(PVP-氧化铝)与实施例2(PVP-氧化锌)的电容器其电容量微降约2.7%,100kHz ESR略增15%,且无任何电容发生短路或漏电流过高的情况。而比较例3(PVP-氧化钛)的固态电容器虽然具有有机-无机复合物层于介电层上,但电容器其电容量衰退达13.76%,且漏电流高达4080μA,在过电压负载测试中更有20%的电容器发生短路。
综上所述,只有特定组成的有机-无机复合物层如PVP-氧化铝、及PVP-氧化锌等位于介电层上,方可有效提升电容器的耐电压特性。上述有机-无机复合物层可使电容器在过电压负载状况下仍能保持较佳的电容量、阻抗与漏电流特性并可防止电容器发生短路。
比较例4至8与实施例3至4
以67V电化学电解反应处理正极铝箔,形成氧化铝介电层于正极铝箔上。以电化学腐蚀负极碳箔,形成高表面积的负极碳箔。在正极与负极之间夹设隔离纸,再卷绕成固态电解电容器素子(element)。以有机酸水溶液处理上述固态电解电容器素子,以修补破损氧化铝介电层。
将固态电解电容器素子含浸于不同组成的水液(见表3)中,其中PVP的数目平均分子量为约1300000。之后加热至60℃后维持一小时,再加热至125℃后维持一小时以除水,即形成有机-无机复合物层于氧化铝介电层上。
接着将上述固态电解电容器素子含浸于-乙烯二氧噻吩(EDOT)单体及浓度50wt%的甲苯磺酸铁乙醇溶液所组成的混合物中,加热混合物以加速聚合反应。在聚合反应时,最高温可达170℃以确保反应完全。经上述聚合反应后,形成导电性共轭高分子如掺杂的PEDOT于正极与负极之间。接着将此固态电解电容器素子套入铝壳,以橡胶盖封口,完成固态电解电容器制作并进行固态电解电容器的特性测试。最后在125℃下对电容器通以40.5V电流6小时,进行过电压负载测试,其电性如表4与5所列。
表3
表4
*过电压负载测试后的电容器特性已扣除测试过程中发生短路的电容器。
实施例3至4与比较例4至8以67V电化学电解反应所形成氧化铝介电层在未经有机无机保护层处理之前的适合最高工作电压为30V。各组电容器封口后的特性相近。但经40.5V过电压负载测试后,比较例4至6的电容器发生不同程度的短路。比较例5中以氢氧化铝与PVP的组合作为电容保护层,以及比较例6中以硼酸与PVP的组合作为电容保护层,均比比较例4中以纯PVP作为电容保护层的短路率还高。反之,当实施例3中以氢氧化铝、硼酸、与PVP的组合作为电容保护层时,可改善电容器于过电压负载测试的短路情况。另一方面,实施例4中以氧化锌、硼酸、与PVP的组合作为电容保护层亦可改善电容器于过电压负载测试的短路状况。
表5
*过电压负载测试后的电容器特性已扣除测试过程中发生短路的电容器。
如表5所示,当比较例7的以咪唑与PVP组合作为电容保护层时,电容器的特性与过电压负载后的短路情况与比较例4的以纯PVP做为电容保护层的电容器类似。但当比较例8的以咪唑、硼酸、与PVP组合作为电容保护层时,电容器经过电压负载测试后全部短路。综上所述,当硼酸与特定的无机碱(如氧化锌及氢氧化铝)搭配用于电容保护层,可以提升电容器的耐电压特性。然而硼酸单独使用或搭配有机碱(如咪唑)作为电容保护层,则反而降低电容器的耐电压特性。
虽然本发明已以数个实施例披露如上,然而其并非用以限定本发明,任何本领域技术人员,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视权利要求所界定者为准。
Claims (10)
1.一种电容结构,其特征在于,包括:
一正极;
一介电层,位于该正极上;
一有机-无机复合物层,位于该介电层上,其中该有机-无机复合物层是由绝缘高分子与无机物混合而成;
一负极;以及
一导电性共轭高分子电解质,位于该有机-无机复合物层与该负极之间。
2.如权利要求1所述的电容结构,其中该正极包括铝、钽、铌、钛、锆、或上述的合金。
3.如权利要求2所述的电容结构,其中该介电层包括该正极金属元素对应的氧化物。
4.如权利要求1所述的电容结构,其中该有机-无机复合物层包括1重量份的绝缘高分子与100至0.01重量份的无机物。
5.如权利要求4所述的电容结构,其中该绝缘高分子包括含氮高分子、含氧高分子、或上述的混掺物。
6.如权利要求5所述的电容结构,其中该含氮高分子包括聚乙烯吡咯烷酮。
7.如权利要求5所述的电容结构,其中该含氧高分子包括聚氧化乙烯。
8.如权利要求4所述的电容结构,其中该无机物包括氧化铝、氧化锌、硼酸与氧化锌的组合、或硼酸与氢氧化铝的组合。
9.如权利要求1所述的电容结构,其中该负极包括金属箔片。
10.如权利要求1所述的电容结构,其中该导电性共轭高分子电解质包含掺杂的聚噻吩、聚吡咯、聚苯胺、或聚(3,4-乙烯二氧噻吩)。
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US10381166B2 (en) * | 2016-05-25 | 2019-08-13 | Vishay Sprague, Inc. | High performance and reliability solid electrolytic tantalum capacitors and screening method |
CN113168966B (zh) * | 2018-11-29 | 2024-01-16 | 京瓷Avx元器件公司 | 含有顺序气相沉积的电介质膜的固体电解电容器 |
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