US20160247633A1 - Oxidant mixture for conjugated polymer synthesis - Google Patents
Oxidant mixture for conjugated polymer synthesis Download PDFInfo
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- US20160247633A1 US20160247633A1 US15/141,840 US201615141840A US2016247633A1 US 20160247633 A1 US20160247633 A1 US 20160247633A1 US 201615141840 A US201615141840 A US 201615141840A US 2016247633 A1 US2016247633 A1 US 2016247633A1
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- electrolytic capacitor
- oxidant
- solid electrolytic
- compound
- oxidant mixture
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- 239000007800 oxidant agent Substances 0.000 title claims abstract description 109
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 6
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 44
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 32
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 73
- 239000002202 Polyethylene glycol Substances 0.000 claims description 53
- 229920001223 polyethylene glycol Polymers 0.000 claims description 53
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 22
- 229920001451 polypropylene glycol Polymers 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 claims description 2
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 description 138
- 239000007787 solid Substances 0.000 description 126
- 230000003068 static effect Effects 0.000 description 72
- 230000000694 effects Effects 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229920001940 conductive polymer Polymers 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 12
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 10
- 230000002195 synergetic effect Effects 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 229960002317 succinimide Drugs 0.000 description 6
- AJAVMTJTPWMHAE-UHFFFAOYSA-N 1h-imidazole;methanol Chemical compound OC.C1=CNC=N1 AJAVMTJTPWMHAE-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 C.C.C*OC Chemical compound C.C.C*OC 0.000 description 2
- 239000004743 Polypropylene 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
- 150000001408 amides Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- XPTXCFGPSNNCAO-UHFFFAOYSA-N CC(N)COCC(C)N.[H]N(C(C)=O)C(C)COCC(C)N([H])C(=O)CCC(=O)N([H])C(C)COCC(C)N([H])C(C)=O Chemical compound CC(N)COCC(C)N.[H]N(C(C)=O)C(C)COCC(C)N([H])C(=O)CCC(=O)N([H])C(C)COCC(C)N([H])C(C)=O XPTXCFGPSNNCAO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- FZYTUSFEOLVWNK-UHFFFAOYSA-N acetamide;methanol Chemical compound OC.CC(N)=O FZYTUSFEOLVWNK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- OMNRDWDFSMCBLP-UHFFFAOYSA-N butan-1-ol;1h-imidazole Chemical compound CCCCO.C1=CNC=N1 OMNRDWDFSMCBLP-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- BVAZPOOMFWFTOL-UHFFFAOYSA-N ethyl carbamate;methanol Chemical compound OC.CCOC(N)=O BVAZPOOMFWFTOL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YEYZNBKNDWPFSQ-UHFFFAOYSA-N methanol;urea Chemical compound OC.NC(N)=O YEYZNBKNDWPFSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- 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
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- 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
- H01G9/145—Liquid electrolytic capacitors
-
- 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
Definitions
- the technical field relates to an electrolyte mixture, an electrolytic capacitor having the same and an oxidant mixture for conjugated polymer synthesis.
- the electrolyte with a high conductivity can reduce the equivalent series resistance (ESR) of the electrolytic capacitor, so as to provide high-frequency low impedance and high reliability.
- a conductive polymer has a higher conductivity than an aqueous electrolyte or a solid organic semiconductor complex salt (e.g. tetracyanoquinodimethane (TCNQ) complex salt) used for conventional capacitors, and exhibits an adequate insulating property at high temperature. Therefore, such conductive polymer has become the mainstream of the solid electrolyte for existing electrolytic capacitors.
- TCNQ tetracyanoquinodimethane
- the conductive polymer as an electrolyte of an electrolytic capacitor provides low impedance and good thermal stability.
- the static capacitance of the electrolytic capacitor having the conductive polymer as an electrolyte is usually lower than that of the conventional aqueous electrolytic capacitor with similar size. The lower static capacitance has become the main drawback of the solid electrolytic capacitor.
- One of exemplary embodiments at least includes an oxidant mixture for conjugated polymer synthesis, and the oxidant mixture at least includes an oxidant, a polyether and a nitrogen-containing compound, or at least include the oxidant, the polyether and a nitrogen-containing polymer, or at least include the oxidant and a polyether compound with nitrogen-containing functional groups, wherein the oxidant mixture and a precursor of a monomer of a conjugated polymer are polymerized directly on a surfac of a dielectric layer.
- FIG. 1 is a process flow of a method of fabricating a solid electrolytic capacitor according to an exemplary embodiment.
- One of exemplary embodiments provides a solid electrolytic capacitor, such as a solid electrolytic capacitor having a conductive polymer as an electrolyte, in which a conductive polymer mixture as a solid electrolyte is polymerized from a monomer of a conjugated polymer and an oxidant mixture.
- the monomer of the conjugated polymer includes thiophene, a thiophene derivative, pyrrole, a pyrrole derivative, aniline, an aniline derivative, or a combination thereof.
- the monomer of the conjugated polymer includes 3,4-ethylenedioxythiophene.
- the oxidant mixture at least includes an oxidant, a polyether, and a nitrogen-containing compound or a nitrogen-containing polymer, or at least includes the oxidant and a polyether with nitrogen-containing functional groups.
- the oxidant includes a ferric ion-containing salt, a copper ion-containing salt, or a persulfate.
- the ferric ion-containing salt includes ferric sulfate, ferric p-toluenesulfonate, ferric chloride, ferric nitriate, ferric perchlorate, or a combination thereof.
- the persulfate includes sodium persulfate, ammonium persulfate, or a combination thereof.
- the polyether at least has a repeating unit structure represented by the following formula:
- R is a linear or branched aliphatic structure, or a liner or branched aromatic structure; and n is from 1 to 1000.
- the polyether includes polyethylene glycol (PEG), a polyethylene glycol copolymer, polyethylene oxide (PEO), a polyethylene oxide copolymer, polypropylene glycol (PPG), a polypropylene glycol copolymer, polyoxymethylene, a polyoxymethylene copolymer, polyphenylene oxide, a polyphenylene oxide copolymer, or a combination thereof.
- the nitrogen-containing compound includes an imidazole compound, an imidazole derivative, an imidazoline compound, an imidazoline derivative, an urea compound, an urea derivative, an urethane compound, an urethane derivative, an imide compound, an imide derivative, an amide compound, an amide derivative, a pyridine compound, a pyridine derviative, a malamine compound, a malamine derivative, a triazole compound, a triazole derivative, or a combination thereof.
- the nitrogen-containing polymer includes polyacrylamide, polyvinyl pyrrolidone, polyvinyl pyridine, polyethyleneimine, polyamide, polyimide, a secondary amine-containing polymer, a tertiary amine-containing polymer, a quaternary amine-containing polymer, or a combination thereof.
- the amount ratio of components of the electrolyte mixture is not limited herein.
- the monomer of the conductive polymer and the oxidant are in a molar ratio of 2.5:1 to 1:2.5.
- the amount ratio of components of the oxidant mixture, the molecular weight of the polyether, and the molecular weight of the nitrogen-containing polymer are not limited herein.
- the amount of the polyether in order to provide an adequate liquid viscosity for the following reaction and fabrication of the capacitor, is not higher than 50 wt % of the oxidant mixture, the amount of an oxidant in the oxidant mixture is not higher than 70 wt % of the oxidant mixture.
- the nitrogen-containing compound or the repeating units of the nitrogen-containing polymer or nitrogen-containing functional groups of the nitrogen-containing polyether to the oxidant are in a molar ratio of no more than 2.
- the conductive polymer mixture as a solid electrolyte polymerized from the monomer of the conjugated polymer and the oxidant mixture at least includes a conjugated polymer, a polyether and a nitrogen-containing compound, or at least includes the conjugated polymer, the polyether and a nitrogen containing polymer, or at least includes the conjugated polymer and a polyether with nitrogen-containing functional groups.
- the conjugated polymer includes polythiophene, a polythiophene derivative, polypyrrole, a polypyrrole derivative, polyaniline, a polyaniline derivative, or a combination thereof.
- the polyether and the nitrogen-containing compound are the same as those described above.
- the conductive polymer mixture as a solid electrolyte includes 10 wt % to 50 wt % of the conjugated polymer, 7 wt % to 40 wt % of the polyether, and 1.5 wt % to 10 wt % of the nitrogen-containing compound.
- the conductive polymer mixture as a solid electrolyte includes 10 wt % to 50 wt % of the conjugated polymer, 7 wt % to 40 wt % of the polyether, and 1.5 wt % to 10 wt % of the nitrogen-containing polymer.
- p-toluenesulfonic acid as a doping agent can be added to provide better conductive properties for the solid electrolyte mixture
- tetrahydrofuran THF
- the mixing sequence of components can be adjusted upon the actual requirement.
- the polyether and the nitrogen-containing compound can be mixed with the monomer, and the oxidant is then added thereto to initiate the polymerization reaction.
- FIG. 1 is a process flow of a method of fabricating a solid electrolytic capacitor according to an exemplary embodiment.
- a method of fabricating a solid electrolytic capacitor includes implementing a step 10 , in which an anode aluminium foil with an Al 2 O 3 dielectric layer and a cathode aluminium foil are wound together with an interposed separator, so as to fabricate a solid electrolytic capacitor element.
- the solid electrolytic capacitor element is subjected to an electrochemical reforming, in which the surface of the metal electrode is oxidized by an electrochemical electrolysis reaction to form a metal oxide dielectric layer on the anode.
- a step 20 is implemented to dip the solid electrolytic capacitor element in the monomer solution of the conjugated polymer and the oxidant mixture solution.
- a step 30 is implemented to carry out a polymerization at elevated temperature, in which a polymerization reaction is accelerated with increasing temperature, so as to form a conductive polymer on the surface of the dielectric layer.
- the conductive polymer serves as an electrolyte mixture of the solid electrolytic capacitor.
- the elevated temperature up to 170° C. maximum is provided to ensure a complete polymerization.
- a step 40 is implemented to perform sealing and aging, in which the solid electrolytic capacitor element is encased in a case, sealed and aged.
- the case is an aluminium case, for example.
- the solid electrolytic capacitor element is sealed with rubber. The solid electrolytic capacitor is thus completed.
- the solid electrolytic capacitor herein can be fabricated with other known methods and the fabricating method thereof is not limited by the said embodiment.
- the oxidant mixture for conjugated polymer synthesis herein can effectively and synergistically increase the static capacitance of the fabricated solid electrolytic capacitor.
- An anode aluminium foil having an Al 2 O 3 dielectric layer formed through an electrochemical reaction at 41V and a cathode aluminium foil having a high surface area caused by electrochemical corrosion were wounded together with an interposed separator, so as to form a solid electrolytic capacitor element.
- the capacitor element was put in an organic acid solution for an electrochemical reforming of the damaged Al 2 O 3 dielectric layer.
- the reforming capacitor element was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 1, respectively.
- EDOT 3,4-ethylenedioxythiophene
- Table 1 3,4-ethylenedioxythiophene
- Example 1 A solid electrolytic capacitor of Example 1 was thus completely fabricated.
- the properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 1 were measured and listed in Table 1.
- the static capacitance of the solid electrolytic capacitor is increased up to 246 ⁇ F; that is, the co-existence of polyethylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively and synergistically enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 2, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 2.
- EDOT 3,4-ethylenedioxythiophene
- Table 2 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 2 were measured and listed in Table 2.
- the static capacitance of the solid electrolytic capacitor is increased up to 250 ⁇ F; that is, the co-existence of polyethylene glycol and 2-methyl imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and 2-methyl imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 3, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 3.
- EDOT 3,4-ethylenedioxythiophene
- Table 3 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 3 were measured and listed in Table 3.
- the static capacitance of the solid electrolytic capacitor is increased up to 223 ⁇ F; that is, the co-existence of polyethylene glycol and urea has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and urea can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 4, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 4.
- EDOT 3,4-ethylenedioxythiophene
- Table 4 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 4 were measured and listed in Table 4.
- the static capacitance of the solid electrolytic capacitor is increased up to 230 ⁇ F; that is, the co-existence of polyethylene glycol and urethane has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and urethane can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 5, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 5.
- the properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 5 were measured and listed in Table 5.
- the static capacitance of the solid electrolytic capacitor is increased up to 233 ⁇ F; that is, the co-existence of polyethylene glycol and succinimide has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and succinimide can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 6, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 6.
- EDOT 3,4-ethylenedioxythiophene
- Table 6 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 6 were measured and listed in Table 6.
- the static capacitance of the solid electrolytic capacitor is increased up to 233 ⁇ F; that is, the co-existence of polyethylene glycol and N-methyl acetamide has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polyethylene glycol and N-methyl acetamide can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 7, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 7.
- EDOT 3,4-ethylenedioxythiophene
- Table 7 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 7 were measured and listed in Table 7.
- the static capacitance of the solid electrolytic capacitor is increased up to 218 ⁇ F; that is, the co-existence of polypropylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that the co-existence of polypropylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 8, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 8.
- EDOT 3,4-ethylenedioxythiophene
- Table 8 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 8 were measured and listed in Table 8.
- a polymer formed from a polyether and a nitrogen-compound can function as polypropylene glycol and N-methyl acetamide mixed each other in the oxidant solution, both of which can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 9, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 9.
- EDOT 3,4-ethylenedioxythiophene
- Table 9 The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 9 were measured and listed in Table 9.
- a solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 10, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 10.
- the properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 10 were measured and listed in Table 10.
- the effect of polyethylene glycol and imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 10. It is found that the static capacitance of the solid electrolytic capacitor is decreased from 10.12 ⁇ F to 5.21 ⁇ F by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly increased to 13.28 ⁇ F by addition of only imidazole to the oxidant solution.
- the static capacitance of the solid electrolytic capacitor is increased up to 93.25 ⁇ F; that is, when the oxidant solution includes copper p-toluene-sulfonate, the co-existence of polyethylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor.
- the results show that when the oxidant solution includes copper p-toluene-sulfonate, the co-existence of polyethylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
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Abstract
An oxidant mixture for conjugated polymer synthesis is provided. The oxidant mixture at least includes an oxidant, a polyether and a nitrogen-containing compound, or at least include the oxidant, the polyether and a nitrogen-containing polymer, or at least include the oxidant and a polyether compound with nitrogen-containing functional groups, wherein the oxidant mixture and a precursor of a monomer of a conjugated polymer are polymerized directly on a surfac of a dielectric layer.
Description
- This application is a divisional application of and claims the priority benefit of U.S. application Ser. No. 13/951,470, filed on Jul. 26, 2013, now allowed, which claims the priority benefit of Taiwan application serial no. 101127060, filed on Jul. 26, 2012. The entirety of each of the above-mentioned patent applications is hereby incorporated by reference herein and made a part of this specification.
- 1. Technical Field
- The technical field relates to an electrolyte mixture, an electrolytic capacitor having the same and an oxidant mixture for conjugated polymer synthesis.
- 2. Background
- Improving the electrolyte conductivity has long been one of the major topics in the development of an electrolytic capacitor. The electrolyte with a high conductivity can reduce the equivalent series resistance (ESR) of the electrolytic capacitor, so as to provide high-frequency low impedance and high reliability. A conductive polymer has a higher conductivity than an aqueous electrolyte or a solid organic semiconductor complex salt (e.g. tetracyanoquinodimethane (TCNQ) complex salt) used for conventional capacitors, and exhibits an adequate insulating property at high temperature. Therefore, such conductive polymer has become the mainstream of the solid electrolyte for existing electrolytic capacitors.
- As compared to the conventional aqueous electrolyte, the conductive polymer as an electrolyte of an electrolytic capacitor provides low impedance and good thermal stability. However, the static capacitance of the electrolytic capacitor having the conductive polymer as an electrolyte is usually lower than that of the conventional aqueous electrolytic capacitor with similar size. The lower static capacitance has become the main drawback of the solid electrolytic capacitor.
- One of exemplary embodiments at least includes an oxidant mixture for conjugated polymer synthesis, and the oxidant mixture at least includes an oxidant, a polyether and a nitrogen-containing compound, or at least include the oxidant, the polyether and a nitrogen-containing polymer, or at least include the oxidant and a polyether compound with nitrogen-containing functional groups, wherein the oxidant mixture and a precursor of a monomer of a conjugated polymer are polymerized directly on a surfac of a dielectric layer.
- Several exemplary embodiments accompanied with FIGURES are described in detail below to further describe the disclosure in details.
- The accompanying drawings are included to provide further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments and, together with the description, serve to explain the principles of the disclosure.
-
FIG. 1 is a process flow of a method of fabricating a solid electrolytic capacitor according to an exemplary embodiment. - One of exemplary embodiments provides a solid electrolytic capacitor, such as a solid electrolytic capacitor having a conductive polymer as an electrolyte, in which a conductive polymer mixture as a solid electrolyte is polymerized from a monomer of a conjugated polymer and an oxidant mixture.
- The monomer of the conjugated polymer includes thiophene, a thiophene derivative, pyrrole, a pyrrole derivative, aniline, an aniline derivative, or a combination thereof. In an embodiment, the monomer of the conjugated polymer includes 3,4-ethylenedioxythiophene.
- The oxidant mixture at least includes an oxidant, a polyether, and a nitrogen-containing compound or a nitrogen-containing polymer, or at least includes the oxidant and a polyether with nitrogen-containing functional groups.
- The oxidant includes a ferric ion-containing salt, a copper ion-containing salt, or a persulfate. The ferric ion-containing salt includes ferric sulfate, ferric p-toluenesulfonate, ferric chloride, ferric nitriate, ferric perchlorate, or a combination thereof. The persulfate includes sodium persulfate, ammonium persulfate, or a combination thereof.
- The polyether at least has a repeating unit structure represented by the following formula:
- wherein R is a linear or branched aliphatic structure, or a liner or branched aromatic structure; and n is from 1 to 1000.
- The polyether includes polyethylene glycol (PEG), a polyethylene glycol copolymer, polyethylene oxide (PEO), a polyethylene oxide copolymer, polypropylene glycol (PPG), a polypropylene glycol copolymer, polyoxymethylene, a polyoxymethylene copolymer, polyphenylene oxide, a polyphenylene oxide copolymer, or a combination thereof.
- The nitrogen-containing compound includes an imidazole compound, an imidazole derivative, an imidazoline compound, an imidazoline derivative, an urea compound, an urea derivative, an urethane compound, an urethane derivative, an imide compound, an imide derivative, an amide compound, an amide derivative, a pyridine compound, a pyridine derviative, a malamine compound, a malamine derivative, a triazole compound, a triazole derivative, or a combination thereof.
- The nitrogen-containing polymer includes polyacrylamide, polyvinyl pyrrolidone, polyvinyl pyridine, polyethyleneimine, polyamide, polyimide, a secondary amine-containing polymer, a tertiary amine-containing polymer, a quaternary amine-containing polymer, or a combination thereof.
- The amount ratio of components of the electrolyte mixture is not limited herein. In an embodiment, in order to provide better electrolyte properties, the monomer of the conductive polymer and the oxidant are in a molar ratio of 2.5:1 to 1:2.5.
- The amount ratio of components of the oxidant mixture, the molecular weight of the polyether, and the molecular weight of the nitrogen-containing polymer are not limited herein. In an embodiment, in order to provide an adequate liquid viscosity for the following reaction and fabrication of the capacitor, the amount of the polyether is not higher than 50 wt % of the oxidant mixture, the amount of an oxidant in the oxidant mixture is not higher than 70 wt % of the oxidant mixture. Besides, the nitrogen-containing compound or the repeating units of the nitrogen-containing polymer or nitrogen-containing functional groups of the nitrogen-containing polyether to the oxidant are in a molar ratio of no more than 2.
- The conductive polymer mixture as a solid electrolyte polymerized from the monomer of the conjugated polymer and the oxidant mixture at least includes a conjugated polymer, a polyether and a nitrogen-containing compound, or at least includes the conjugated polymer, the polyether and a nitrogen containing polymer, or at least includes the conjugated polymer and a polyether with nitrogen-containing functional groups.
- In the conductive polymer mixture as a solid electrolyte, the conjugated polymer includes polythiophene, a polythiophene derivative, polypyrrole, a polypyrrole derivative, polyaniline, a polyaniline derivative, or a combination thereof.
- In the conductive polymer mixture as a solid electrolyte, the polyether and the nitrogen-containing compound are the same as those described above.
- In an embodiment, the conductive polymer mixture as a solid electrolyte includes 10 wt % to 50 wt % of the conjugated polymer, 7 wt % to 40 wt % of the polyether, and 1.5 wt % to 10 wt % of the nitrogen-containing compound. In another embodiment, the conductive polymer mixture as a solid electrolyte includes 10 wt % to 50 wt % of the conjugated polymer, 7 wt % to 40 wt % of the polyether, and 1.5 wt % to 10 wt % of the nitrogen-containing polymer.
- Other compounds can be added to the formulation and composition of the electrolyte mixture herein, so as to adjust properties to meet various requirements. For example, p-toluenesulfonic acid as a doping agent can be added to provide better conductive properties for the solid electrolyte mixture, or tetrahydrofuran (THF) can be added to improve processing or reaction properties.
- As for the formulation and composition of the electrolyte mixture herein, the mixing sequence of components can be adjusted upon the actual requirement. For example, the polyether and the nitrogen-containing compound can be mixed with the monomer, and the oxidant is then added thereto to initiate the polymerization reaction.
-
FIG. 1 is a process flow of a method of fabricating a solid electrolytic capacitor according to an exemplary embodiment. - Referring to
FIG. 1 , in an embodiment, a method of fabricating a solid electrolytic capacitor includes implementing astep 10, in which an anode aluminium foil with an Al2O3 dielectric layer and a cathode aluminium foil are wound together with an interposed separator, so as to fabricate a solid electrolytic capacitor element. The solid electrolytic capacitor element is subjected to an electrochemical reforming, in which the surface of the metal electrode is oxidized by an electrochemical electrolysis reaction to form a metal oxide dielectric layer on the anode. - Thereafter, a
step 20 is implemented to dip the solid electrolytic capacitor element in the monomer solution of the conjugated polymer and the oxidant mixture solution. - Afterwards, a
step 30 is implemented to carry out a polymerization at elevated temperature, in which a polymerization reaction is accelerated with increasing temperature, so as to form a conductive polymer on the surface of the dielectric layer. The conductive polymer serves as an electrolyte mixture of the solid electrolytic capacitor. The elevated temperature up to 170° C. maximum is provided to ensure a complete polymerization. - Then, a
step 40 is implemented to perform sealing and aging, in which the solid electrolytic capacitor element is encased in a case, sealed and aged. The case is an aluminium case, for example. The solid electrolytic capacitor element is sealed with rubber. The solid electrolytic capacitor is thus completed. - The solid electrolytic capacitor herein can be fabricated with other known methods and the fabricating method thereof is not limited by the said embodiment.
- The oxidant mixture for conjugated polymer synthesis herein can effectively and synergistically increase the static capacitance of the fabricated solid electrolytic capacitor.
- An anode aluminium foil having an Al2O3 dielectric layer formed through an electrochemical reaction at 41V and a cathode aluminium foil having a high surface area caused by electrochemical corrosion were wounded together with an interposed separator, so as to form a solid electrolytic capacitor element. Then, the capacitor element was put in an organic acid solution for an electrochemical reforming of the damaged Al2O3 dielectric layer. The reforming capacitor element was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 1, respectively. A polymerization reaction was then accelerated at elevated temperature up to 170° C. maximum to ensure a complete polymerization. Thereafter, the capacitor element was encased in an aluminum case, sealed with rubber, and aged at 125° C. with an applied voltage of 16 V to lower the leakage current of the capacitor. A solid electrolytic capacitor of Example 1 was thus completely fabricated. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 1 were measured and listed in Table 1.
-
TABLE 1 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* imidazole methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 2.99 47.01 Average 168.15 10.52 5.13 Std. 2.67 0.30 2.82 4 50 10 2.99 37.01 Average 246.08 9.61 2.92 Std. 2.86 0.40 1.22 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 1. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 168 μF by addition of only imidazole to the oxidant solution; that is, imidazole alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and imidazole are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 246 μF; that is, the co-existence of polyethylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively and synergistically enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 2, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 2. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 2 were measured and listed in Table 2.
-
TABLE 2 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene 2-methyl Capacitance ESR LC # sulfonate glycol* imidazole methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 3.60 46.4 Average 181.07 11.71 3.21 Std. 3.17 0.69 1.88 4 50 10 3.60 36.4 Average 250.14 9.44 4.03 Std. 2.93 0.29 2.68 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and 2-methyl imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 2. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is maintained at 181 μF by addition of only 2-methyl imidazole to the oxidant solution; that is, 2-methyl imidazole alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and 2-methyl imidazole are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 250 μF; that is, the co-existence of polyethylene glycol and 2-methyl imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and 2-methyl imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 3, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 3. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 3 were measured and listed in Table 3.
-
TABLE 3 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* urea methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 2.64 47.56 Average 164.22 10.91 17.65 Std. 2.63 0.31 14.84 4 50 10 2.64 37.56 Average 223.04 9.87 3.87 Std. 2.05 0.38 2.75 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and urea to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 3. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 164 μF by addition of only urea to the oxidant solution; that is, urea alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and urea are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 223 μF; that is, the co-existence of polyethylene glycol and urea has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and urea can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 4, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 4. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 4 were measured and listed in Table 4.
-
TABLE 4 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* urethane methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 7.82 42.18 Average 175.81 10.57 35.73 Std. 4.15 0.65 26.33 4 50 10 7.82 32.18 Average 230.37 8.70 1.91 Std. 1.60 0.40 0.91 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and urethane to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 4. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 176 μF by addition of only urethane to the oxidant solution; that is, urethane alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and urethane are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 230 μF; that is, the co-existence of polyethylene glycol and urethane has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and urethane can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 5, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 5. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 5 were measured and listed in Table 5.
-
TABLE 5 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* succinimide methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 8.70 41.30 Average 163.77 9.06 14.89 Std. 2.21 0.35 4.17 4 50 10 8.70 31.30 Average 232.68 9.01 2.64 Std. 3.82 0.23 2.18 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and succinimide to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 5. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 164 μF by addition of only succinimide to the oxidant solution; that is, succinimide alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and succinimide are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 233 μF; that is, the co-existence of polyethylene glycol and succinimide has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and succinimide can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 6, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 6. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 6 were measured and listed in Table 6.
-
TABLE 6 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene N-methyl Capacitance ESR LC # sulfonate glycol* acetamide methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 210.03 9.51 6.78 Std. 2.21 0.38 5.45 3 50 — 3.21 46.79 Average 158.24 9.55 12.68 Std. 1.79 0.47 8.43 4 50 10 3.21 36.79 Average 233.06 8.88 3.42 Std. 2.76 0.36 1.47 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and N-methyl acetamide to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 6. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 210 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 158 μF by addition of only N-methyl acetamide to the oxidant solution; that is, N-methyl acetamide alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and N-methyl acetamide are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 233 μF; that is, the co-existence of polyethylene glycol and N-methyl acetamide has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polyethylene glycol and N-methyl acetamide can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 7, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 7. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 7 were measured and listed in Table 7.
-
TABLE 7 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polypropylene Capacitance ESR LC # sulfonate glycol* imidazole methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 — 40 Average 185.63 8.68 17.67 Std. 3.05 0.40 18.68 3 50 — 2.99 47.01 Average 168.15 10.52 5.13 Std. 2.67 0.30 2.82 4 50 10 2.99 37.01 Average 218.42 8.75 38.68 Std. 2.92 0.30 35.84 *The molecular weight of polypropylene glycol is 1000. - The effect of polypropylene glycol and imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 7. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 185 μF by addition of polypropylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 168 μF by addition of only imidazole to the oxidant solution; that is, imidazole alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polypropylene glycol and imidazole are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 218 μF; that is, the co-existence of polypropylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that the co-existence of polypropylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- Jeffamine® D230 (represented by formula I below) as a diamine compound available from Huntsman Corporation and succinic acid were mixed in a molar ratio of 5:4, and reacted completely under nitrogen at 160° C. Excessive acetic acid was added thereto, and the resulting solution was refluxed and reacted at the same temperature until the reaction was completed. The generated water and the remaining acetic acid were removed by heating under reduced pressure. Therefore, a polyether-amide copolymer having a molecular weight of 1500 (polyoxypropylene-amide in Table 8 represented by formula II below) was obtained. The copolymer was added to the oxidant solution according to the amount ratio of Table 8.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 8, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 8. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 8 were measured and listed in Table 8.
-
TABLE 8 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric polyoxy- 100 kHz p-toluene- polypropylene N-methyl propylene- Capacitance ESR LC # sulfonate glycol* acetamide amide methanol (μF) (mΩ) (μA) 1 50 — 50 Average 180.14 10.59 9.57 Std. 1.77 0.55 4.30 2 50 10 40 Average 185.63 8.68 17.67 Std. 3.05 0.40 18.68 3 50 10 7.5 — 32.5 Average 224.63 10.19 3.71 Std. 2.65 0.28 1.72 4 50 — — 17.5 32.5 Average 224.91 9.58 2.72 Std. 5.55 0.37 1.09 *The molecular weight of polypropylene glycol is 1000. - The effect of polypropylene glycol and polyoxypropylene-amide copolymer to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 8. It is found that the static capacitance of the solid electrolytic capacitor is increased from 180 μF to 185 μF by addition of polypropylene glycol to the oxidant solution. However, when both polypropylene glycol and N-methyl acetamide are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is greatly enhanced from 180 μF to 224 μF. It is also found that when polyoxypropylene-amide is used instead of polypropylene glycol and N-methyl acetamide, the static capacitance of the solid electrolytic capacitor is still maintained at 224 μF. The results show that the addition of polyoxypropylene-amide or addition of both polypropylene glycol and N-methyl acetamide has the same effect on improvement of the static capacitance of the solid electrolytic capacitor.
- In view of the results, a polymer formed from a polyether and a nitrogen-compound can function as polypropylene glycol and N-methyl acetamide mixed each other in the oxidant solution, both of which can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 9, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 9. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 9 were measured and listed in Table 9.
-
TABLE 9 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties ferric 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* imidazole 1-butanol (μF) (mΩ) (μA) 1 40 — — 60 Average 187.91 12.64 20.67 Std. 2.70 0.49 14.70 2 40 10 — 50 Average 211.86 10.16 5.05 Std. 2.79 0.41 4.26 3 40 — 2.39 57.61 Average 174.35 14.80 10.98 Std. 2.77 0.49 6.09 4 40 10 2.39 47.61 Average 236.29 11.84 2.33 Std. 4.69 0.55 1.58 *The molecular weight of polyethylene glycol is 1000. - The effect of polyethylene glycol and imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 9. It is found that the static capacitance of the solid electrolytic capacitor is increased from 187 μF to 211 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly reduced to 174 μF by addition of only imidazole to the oxidant solution; that is, imidazole alone in the oxidant solution does not improve the static capacitance of the solid electrolytic capacitor. However, when both polyethylene glycol and imidazole are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 236 μF. The results show that the co-existence of polyethylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced. Besides, by comparison with Example 1, it is proved that the synergistic effect of the co-existence of polyethylene glycol and imidazole on improvement of the static capacitance of the solid electrolytic capacitor works in different solvent systems.
- A solid electrolytic capacitor element fabricated according to the manner of Example 1 was dipped in a monomer solution of 3,4-ethylenedioxythiophene (EDOT) and an oxidant solution listed in Table 10, followed by polymerization, sealing and charge aging with reference to the conditions of Example 1, so as to form a solid electrolytic capacitor of Example 10. The properties such as static capacitance, 100 kHz equivalent series resistance (ESR), leakage current (LC) of each solid electrolytic capacitor of Example 10 were measured and listed in Table 10.
-
TABLE 10 Composition of oxidant solution (wt %) Solid electrolytic capacitor properties copper 100 kHz p-toluene- polyethylene Capacitance ESR LC # sulfonate glycol* imidazole methanol (μF) (mΩ) (μA) 1 50 — — 50 Average 10.12 276.85 0.93 Std. 3.62 172.79 0.20 2 50 10 — 40 Average 5.21 81.30 4.93 Std. 1.99 32.00 0.42 3 50 — 4.20 45.80 Average 13.28 63.84 1.64 Std. 1.17 7.36 0.69 4 50 10 4.20 35.80 Average 93.25 1.15 2.03 Std. 5.99 0.12 0.29 *The molecular weight of polyethylene glycol is 1000. - When the oxidant solution includes copper p-toluene-sulfonate, the effect of polyethylene glycol and imidazole to the solid electrolytic capacitor is shown in the solid electrolytic capacitor properties listed in Table 10. It is found that the static capacitance of the solid electrolytic capacitor is decreased from 10.12 μF to 5.21 μF by addition of polyethylene glycol to the oxidant solution. It is also found that the static capacitance is slightly increased to 13.28 μF by addition of only imidazole to the oxidant solution. However, when both polyethylene glycol and imidazole are present in the oxidant solution, the static capacitance of the solid electrolytic capacitor is increased up to 93.25 μF; that is, when the oxidant solution includes copper p-toluene-sulfonate, the co-existence of polyethylene glycol and imidazole has a synergistic effect on improvement of the static capacitance of the solid electrolytic capacitor. The results show that when the oxidant solution includes copper p-toluene-sulfonate, the co-existence of polyethylene glycol and imidazole can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- In view of the foregoing, when a polyether and a nitrogen-containing compound or a nitrogen-containing polymer are present in the oxidant solution, or when a polyether with nitrogen-containing functional groups is present in the oxidant solution, each of which can achieve an unexpected effect, and therefore the static capacitance of the solid electrolytic capacitor can be affectively enhanced.
- It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims and their equivalents.
Claims (10)
1. An oxidant mixture for conjugated polymer synthesis, at least comprising an oxidant, a polyether and a nitrogen-containing compound, or at least comprising the oxidant, the polyether and a nitrogen-containing polymer, or at least comprising the oxidant and a polyether compound with nitrogen-containing functional groups,
wherein the oxidant mixture and a precursor of a monomer of a conjugated polymer are polymerized directly on a surfac of a dielectric layer.
2. The oxidant mixture of claim 1 , wherein the oxidant is selected from the group consisting of a ferric ion-containing salt, a copper ion-containing salt and a persulfate.
3. The oxidant mixture of claim 2 , wherein the ferric ion-containing salt is selected from the group consisting of ferric sulfate, ferric p-toluenesulfonate, ferric chloride, ferric nitriate, ferric perchlorate and combinations thereof.
4. The oxidant mixture of claim 2 , wherein the persulfate is selected from the group consisting of sodium persulfate, ammonium persulfate and combinations thereof.
6. The oxidant mixture of claim 1 , wherein the polyether is selected from the group consisting of polyethylene glycol, a polyethylene glycol copolymer, polyethylene oxide, a polyethylene oxide copolymer, polypropylene glycol, a polypropylene glycol copolymer, polyoxymethylene, a polyoxymethylene copolymer, polyphenylene oxide, a polyphenylene oxide copolymer and combinations thereof.
7. The oxidant mixture of claim 1 , wherein the nitrogen-containing compound is selected from the group consisting of an imidazole compound, an imidazoline compound, an urethane compound, an imide compound, an amide compound, an urea compound, a pyridine compound, a malamine compound, a triazole compound and combinations thereof.
8. The oxidant mixture of claim 1 , wherein the nitrogen-containing polymer is selected from the group consisting of polyacrylamide, polyvinyl pyrrolidone, polyvinyl pyridine, polyethyleneimine, polyamide, polyimide, a secondary amine-containing polymer, a tertiary amine-containing polymer, a quaternary amine-containing polymer and combinations thereof.
9. The oxidant mixture of claim 1 , wherein the monomer of the conjugated polymer is selected from the group consisting of thiophene, a thiophene derivative, pyrrole, a pyrrole derivative, aniline, an aniline derivative and combinations thereof.
10. The oxidant mixture of claim 1 , wherein the monomer of the conjugated polymer comprises 3,4-ethylenedioxythiophene.
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US13/951,470 US9355785B2 (en) | 2012-07-26 | 2013-07-26 | Electrolyte mixture, electrolytic capacitor having the same and oxidant mixture for conjugated polymer synthesis |
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CN105111416B (en) * | 2015-09-22 | 2017-08-04 | 东莞市富默克化工有限公司 | A kind of plated conductive polymer and preparation method thereof |
TWI602206B (en) * | 2015-12-28 | 2017-10-11 | 財團法人工業技術研究院 | Capacitor structure |
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CN110707355B (en) * | 2019-10-09 | 2021-01-15 | 北京工业大学 | All-solid-state polyelectrolyte diaphragm and preparation method thereof |
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CN112133562B (en) * | 2020-09-29 | 2022-04-08 | 常州华威电子有限公司 | High-temperature-resistant aluminum electrolytic capacitor electrolyte with long service life |
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