WO2021121174A1 - 一种组合物、电容器用聚合物及电容器 - Google Patents
一种组合物、电容器用聚合物及电容器 Download PDFInfo
- Publication number
- WO2021121174A1 WO2021121174A1 PCT/CN2020/136011 CN2020136011W WO2021121174A1 WO 2021121174 A1 WO2021121174 A1 WO 2021121174A1 CN 2020136011 W CN2020136011 W CN 2020136011W WO 2021121174 A1 WO2021121174 A1 WO 2021121174A1
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- WO
- WIPO (PCT)
- Prior art keywords
- phosphate
- capacitor
- ethylenedioxythiophene
- polymer
- composition
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- -1 phosphate compound Chemical class 0.000 claims abstract description 23
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 22
- 239000010452 phosphate Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 claims description 4
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 4
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 claims description 3
- QVKQJEWZVQFGIY-UHFFFAOYSA-N dipropyl hydrogen phosphate Chemical compound CCCOP(O)(=O)OCCC QVKQJEWZVQFGIY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- WGKIXRIZQOQWTB-UHFFFAOYSA-N ethyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylate Chemical compound O1CCOC2=C(C(=O)OCC)SC=C21 WGKIXRIZQOQWTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 claims description 3
- BTVLERZSQCGLGL-UHFFFAOYSA-N CC(C)OC(=O)C1=C2C(=CS1)OCCO2 Chemical compound CC(C)OC(=O)C1=C2C(=CS1)OCCO2 BTVLERZSQCGLGL-UHFFFAOYSA-N 0.000 claims description 2
- MLXAPRJMRAWNHH-UHFFFAOYSA-N CCCCOC(=O)C1=C2C(=CS1)OCCO2 Chemical compound CCCCOC(=O)C1=C2C(=CS1)OCCO2 MLXAPRJMRAWNHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- XMNQCSOOUOJOLR-UHFFFAOYSA-M ethyl methyl phosphate Chemical compound CCOP([O-])(=O)OC XMNQCSOOUOJOLR-UHFFFAOYSA-M 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- DEZUSZMWEWAYSI-UHFFFAOYSA-N methyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylate Chemical compound O1CCOC2=C(C(=O)OC)SC=C21 DEZUSZMWEWAYSI-UHFFFAOYSA-N 0.000 claims description 2
- RUIKQPWKVGWNHX-UHFFFAOYSA-N CCCOC(C1=C2OCCOC2=CS1)=O Chemical compound CCCOC(C1=C2OCCOC2=CS1)=O RUIKQPWKVGWNHX-UHFFFAOYSA-N 0.000 claims 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 239000011888 foil Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000004815 dispersion polymer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 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 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DCCRIIFBJZOPAV-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylic acid Chemical compound O1CCOC2=C(C(=O)O)SC=C21 DCCRIIFBJZOPAV-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XMNQCSOOUOJOLR-UHFFFAOYSA-N ethyl methyl hydrogen phosphate Chemical compound CCOP(O)(=O)OC XMNQCSOOUOJOLR-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- H01G9/004—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
- H01G9/15—Solid electrolytic capacitors
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3242—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
Definitions
- the invention belongs to the technical field of solid capacitor materials, and specifically relates to a composition, a polymer for capacitors and a capacitor.
- Solid electrolytic capacitors use conductive polymer with high conductivity and good thermal stability as the electrolyte. Compared with conventional liquid electrolytic capacitors, it has the characteristics of good reliability, long service life, high frequency and low impedance, and large ripple current resistance. Overcome the shortcomings of liquid electrolytic capacitor electrolyte leakage. With the rapid development of the domestic electronic information industry, from the development trend in recent years, solid electrolytic capacitors will gradually replace liquid low-voltage electrolytic capacitors, and will become one of the pillar products of the electronic information industry in the 21st century.
- the withstand voltage of aluminum electrolytic capacitors is directly proportional to the thickness of the aluminum oxide film layer. If the aluminum oxide film layer is thinned, it means that the aluminum foil withstand voltage decreases. When the thickness of the aluminum oxide film layer is reduced to a certain level After the level, the withstand voltage of the positive electrode foil will not meet the performance requirements, and the positive and negative electrodes will be connected during the use of the capacitor, which is the so-called electrical breakdown; if the corrosion has not reached the above severe conditions, the leakage current will be too large .
- solid aluminum electrolytic capacitors generally use poly-3,4-ethylenedioxythiophene (PEDOT) polymer materials prepared with 3,4-ethylenedioxythiophene as a monomer. Because the above-mentioned polymer materials have good electrical conductivity and excellent environmental stability, they are widely used as solid electrolytic capacitor cathodes. However, since the strong acidic substances used in the polymerization reaction often remain in the resulting polymer materials, when the capacitor is used, it will corrode the oxide film layer of the aluminum foil and cause it to become thinner, which will cause the problem of a decrease in the capacitor's withstand voltage and an increase in leakage current. Therefore, the withstand voltage and leakage current performance of solid aluminum electrolytic capacitors prepared solely using 3,4-ethylenedioxythiophene monomer can no longer meet the increasing demands of people.
- PEDOT poly-3,4-ethylenedioxythiophene
- the present invention provides a composition, a polymer for a capacitor, and a capacitor.
- the present invention provides a composition including a polymerized monomer, a phosphate compound and a capping agent;
- the polymerized monomers include 3,4-ethylenedioxythiophene polymerized monomers
- the capping agent includes a compound represented by structural formula 1;
- R 4 is selected from H or a hydrocarbon group having 1 to 6 carbon atoms.
- composition includes the following weight components:
- the capping agent includes 3,4-ethylenedioxythiophene-2-methyl carboxylate, 3,4-ethylenedioxythiophene-2-ethyl carboxylate, 3,4-ethylenedioxythiophene-2 -One or more of propyl formate, 3,4-ethylenedioxythiophene-2-isopropyl formate, and 3,4-ethylenedioxythiophene-2-butyl formate.
- the phosphate compound includes a compound represented by structural formula 2;
- R 1 , R 2, and R 3 are each independently selected from a hydrocarbon group having 1 to 6 carbon atoms, an ether group, a carbonyl group, or an aromatic group in which H or a hydrogen atom is substituted or unsubstituted, and R 1 , R 2 and R 3 is not H at the same time.
- R 1 , R 2 and R 3 are connected to each other to form a ring.
- the phosphate compound includes trimethyl phosphate, dimethyl phosphate, ethyl methyl phosphate, triethyl phosphate, diethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate
- esters tripropyl phosphate, tripropynyl phosphate, dipropyl phosphate, tributyl phosphate, dibutyl phosphate, monobutyl phosphate, and tripentyl phosphate.
- the polymerized monomer includes a compound represented by structural formula 3;
- the present invention provides a polymer for capacitors obtained by polymerizing the above-mentioned composition.
- the present invention provides an aluminum electrolytic capacitor including a capacitor element and a cathode material attached to the capacitor element, and the cathode material includes the above-mentioned capacitor polymer.
- the capacitor is a solid aluminum electrolytic capacitor or a solid tantalum electrolytic capacitor.
- the composition provided by the present invention uses a phosphate compound, a polymerizing monomer and a capping agent as polymerization raw materials.
- Phosphate compounds have a certain degree of lubricity and are easy to contact metal foil directly. To a certain extent, they can be used as metal foil slow-release agents to prevent corrosion, repair and protect the oxide film on the metal foil, and significantly reduce capacitors. The occurrence of damage to the oxide film on the metal foil; at the same time, the use of the compound shown in structural formula 1 as the end-capping agent can reduce the degree of polymerization in the polymerization reaction of polymerized monomers, slow down the polymerization rate of monomers, thereby reducing the acidity of the system, and further prevent The occurrence of corrosion.
- An embodiment of the present invention provides a composition including a polymerized monomer, a phosphate compound, and a capping agent;
- the polymerized monomers include 3,4-ethylenedioxythiophene polymerized monomers
- the capping agent includes a compound represented by structural formula 1;
- R 4 is selected from H or a hydrocarbon group having 1 to 6 carbon atoms.
- Phosphate compounds have a certain degree of lubricity and are easy to directly contact with metal foil. To a certain extent, they can be used as metal foil slow-release agents to prevent corrosion. It can repair and protect the oxide film on the metal foil. Reduce the occurrence of damage to the oxide film on the capacitor metal foil; at the same time, the use of the compound shown in Structural Formula 1 as the end-capping agent can reduce the degree of polymerization in the polymerization reaction of the polymerized monomer, slow down the polymerization speed of the monomer, and thereby reduce the acidity of the system. Further prevent the occurrence of corrosion.
- the composition includes the following weight components:
- the composition includes the following weight components:
- the addition amount of the phosphate compound is too low, the protective effect on the aluminum foil oxide film is not obvious; if the addition amount of the phosphate compound is too high, the conductivity of the polymer after polymerization will be deteriorated , And the adhesion effect of polymer and metal foil is reduced.
- the addition amount of the end-capping agent is too low, the degree of polymerization of the polymerization reaction is not significantly reduced; if the addition amount of the end-capping agent is too high, the polymerization of the polymer after polymerization is likely to be too low, thereby It affects the structural strength of the polymer and is not conducive to the improvement of the safety performance of the capacitor.
- the capping agent includes methyl 3,4-ethylenedioxythiophene-2-carboxylate, ethyl 3,4-ethylenedioxythiophene-2-carboxylate, 3,4-ethylenedioxythiophene One or more of propyl-2-carboxylate, isopropyl 3,4-ethylenedioxythiophene-2-carboxylate, and butyl 3,4-ethylenedioxythiophene-2-carboxylate.
- the phosphate compound includes a compound represented by structural formula 2;
- R 1 , R 2, and R 3 are each independently selected from H or substituted or unsubstituted hydrocarbon groups with 1 to 6 carbon atoms, ether groups, carbonyl groups or aromatic groups, and the substituents are halogen, hydroxyl or A carboxyl group, and R 1 , R 2 and R 3 are not H at the same time.
- two of R 1 , R 2 and R 3 are connected to each other to form a ring.
- the phosphate compound includes trimethyl phosphate, dimethyl phosphate, methyl ethyl phosphate, triethyl phosphate, diethyl phosphate, dimethyl ethyl phosphate, methyl One or more of diethyl phosphate, tripropyl phosphate, tripropynyl phosphate, dipropyl phosphate, tributyl phosphate, dibutyl phosphate, monobutyl phosphate, and tripentyl phosphate.
- 3,4-ethylenedioxythiophene polymerized monomers refer to 3,4-ethylenedioxythiophene and its derivatives that can undergo polymerization at positions 2 and 5 on the thiophene ring. Things.
- the polymerized monomer includes a compound represented by structural formula 3;
- Another embodiment of the present invention provides a polymer for capacitors, which is obtained by polymerizing the above-mentioned composition.
- the polymer for capacitors obtained by polymerization of the above composition has reduced corrosiveness of the metal foil, can effectively reduce the leakage current of the capacitor, and improve the stability of the performance of the solid capacitor.
- Another embodiment of the present invention provides an aluminum electrolytic capacitor, which includes a capacitor element and a cathode material attached to the capacitor element, and the cathode material includes the capacitor polymer described above.
- the capacitor is a solid aluminum electrolytic capacitor or a solid tantalum electrolytic capacitor.
- This embodiment is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including the following steps:
- an aqueous polymer dispersion is prepared by free radical polymerization.
- the specific implementation process is: take 1753g of water and 90.32g of sodium polystyrene sulfonate, mix them uniformly in a disperser at high speed, under the protection of a nitrogen atmosphere, control the temperature in the reactor to 22°C, and add 17.54g of iron sulfate aqueous solution (1.3 % Concentration) and 7.25 g of the above-mentioned polymerization raw materials, continue to react for 24 hours, and discharge to obtain a polymer dispersion PEDOT/PSS intermediate.
- the polymer dispersion PEDOT:PSS intermediate is mixed with anion and cation exchange resin to remove impurity ions. Take 500 g of the polymer dispersion PEDOT:PSS intermediate from which impurity ions have been removed, add 53.2 g of polyethylene glycol 1000, mix and stir for 8 hours and then homogenize with a homogenizer to obtain a polymer dispersion.
- the dried capacitor element is impregnated with polymer dispersion at room temperature and a vacuum of -0.09MPa for 20 minutes.
- the element is taken out and the polymer dispersion on its surface is wiped off.
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This example is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This embodiment is used to illustrate a composition, a polymer for capacitors, and a method for preparing capacitors disclosed in the present invention, including the following steps:
- the composition was prepared into a 25% monomer solution, the capacitor element was used to impregnate the monomer solution for 2 minutes, the capacitor element was taken out and dried in an oven at 60°C for 30 minutes, and then cooled to room temperature.
- the capacitor element treated by the above steps is impregnated with a 60% concentration of ferric p-toluenesulfonate ethanol oxidant solution under the conditions of normal temperature and a vacuum of -0.085MPa, and the impregnation time is 5 minutes.
- This comparative example is used to compare and illustrate a polymer for capacitors and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This embodiment is used to compare and illustrate a polymer for capacitors and a method for preparing capacitors disclosed in the present invention, including the following operation steps:
- the capacitor element treated by the above steps is impregnated with a 60% concentration of ferric p-toluenesulfonate ethanol oxidant solution under the conditions of normal temperature and a vacuum of -0.085MPa, and the impregnation time is 5 minutes.
- This comparative example is used to compare and illustrate a polymer for capacitors and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- This comparative example is used to compare and illustrate a polymer for capacitors and a method for preparing capacitors disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:
- Example 8 663.4 2.27 7.42 7.3 Comparative example 1 662.2 2.30 7.21 15.2 Comparative example 2 664.2 2.26 7.61 25.7 Comparative example 3 663.1 2.31 7.41 12.5 Comparative example 4 663.5 2.33 7.35 14.2
- the solid electrolytic capacitor prepared by the polymer for capacitors provided by the present invention has a lower leakage current value, the largest is only 7.3 ⁇ A, while the monomer preparation of Comparative Examples 1 to 4
- the leakage current value of the obtained solid electrolytic capacitor is obviously larger, the smallest is 12.5 ⁇ A; it shows that the addition of phosphate ester substances and blocking agent effectively alleviates the corrosion of the solid electrolyte to the aluminum foil, reduces the leakage current of the capacitor, and improves The voltage withstand capability of the capacitor is ensured, thereby ensuring the stability of the performance of the solid electrolytic capacitor, which can greatly increase the service life of the solid electrolytic capacitor.
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Abstract
Description
Cap(μF) | DF(%) | ESR(mΩ) | I LC(μA) | |
实施例1 | 667.4 | 2.28 | 7.34 | 5.8 |
实施例2 | 663.5 | 2.33 | 7.24 | 5.2 |
实施例3 | 657.5 | 2.36 | 7.38 | 3.1 |
实施例4 | 660.7 | 2.34 | 7.37 | 3.6 |
实施例5 | 663.6 | 2.32 | 7.19 | 6.7 |
实施例6 | 661.4 | 2.35 | 7.23 | 6.3 |
实施例7 | 664.4 | 2.28 | 7.28 | 4.7 |
实施例8 | 663.4 | 2.27 | 7.42 | 7.3 |
对比例1 | 662.2 | 2.30 | 7.21 | 15.2 |
对比例2 | 664.2 | 2.26 | 7.61 | 25.7 |
对比例3 | 663.1 | 2.31 | 7.41 | 12.5 |
对比例4 | 663.5 | 2.33 | 7.35 | 14.2 |
Claims (10)
- 根据权利要求1所述的组合物,其特征在于,所述组合物包括以下重量组分:聚合单体96~99.9998份,封端剂0.0001~1份,磷酸酯类化合物0.0001~3份。
- 根据权利要求1所述的组合物,其特征在于,所述封端剂包括3,4-乙烯二氧噻吩-2-甲酸甲酯、3,4-乙烯二氧噻吩-2-甲酸乙酯、3,4-乙烯二氧噻吩-2-甲酸丙酯、3,4-乙烯二氧噻吩-2-甲酸异丙酯、3,4-乙烯二氧噻吩-2-甲酸丁酯中的一种或多种。
- 根据权利要求4所述的组合物,其特征在于,R 1、R 2和R 3中两个相互连接成环。
- 根据权利要求4所述的组合物,其特征在于,所述磷酸酯类化合物包括磷酸三甲酯、磷酸二甲酯、磷酸甲乙酯、磷酸三乙酯、磷酸二乙酯、二甲基乙基磷酸酯、甲基二乙基磷酸酯、磷酸三丙酯、磷酸三丙炔酯、磷酸二丙酯、磷酸三丁酯、磷酸二丁酯、磷酸单丁酯和磷酸三戊酯中的一种或多种。
- 一种电容器用聚合物,其特征在于,由权利要求1~7任意一项所述的组合物聚合得到。
- 一种电容器,其特征在于,包括电容器素子和附着于所述电容器素子上的阴极材料,所述阴极材料包括如权利要求8所述的电容器用聚合物。
- 根据权利要求9所述的电容器,其特征在于,所述电容器为固态铝电解电容器或固态钽电解电容器。
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