WO2020224630A1 - 一种导电聚合物、电容器及其制备方法 - Google Patents

一种导电聚合物、电容器及其制备方法 Download PDF

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WO2020224630A1
WO2020224630A1 PCT/CN2020/089098 CN2020089098W WO2020224630A1 WO 2020224630 A1 WO2020224630 A1 WO 2020224630A1 CN 2020089098 W CN2020089098 W CN 2020089098W WO 2020224630 A1 WO2020224630 A1 WO 2020224630A1
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group
optionally substituted
capacitor
substituted
unsubstituted
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PCT/CN2020/089098
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English (en)
French (fr)
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赵大成
燕民翔
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深圳新宙邦科技股份有限公司
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Priority to US17/603,940 priority Critical patent/US20220195111A1/en
Priority to JP2021562780A priority patent/JP2022529801A/ja
Priority to KR1020217032866A priority patent/KR20220004968A/ko
Publication of WO2020224630A1 publication Critical patent/WO2020224630A1/zh

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    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • 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
    • 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
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
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    • 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
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    • 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
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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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    • 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
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    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • 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
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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Definitions

  • the invention belongs to the technical field of capacitors, and specifically relates to a conductive polymer, a capacitor and a preparation method thereof.
  • solid electrolytic capacitors Compared with ordinary electrolytic capacitors, solid electrolytic capacitors use solid conductive materials with high conductivity and good thermal stability as the electrolyte, which not only has all the characteristics of ordinary electrolytic capacitors, but also has good reliability, long service life, high frequency, low impedance, and resistance. Additional features such as extra large ripple current, and can overcome the shortcomings of liquid electrolytic capacitors that are easy to leak and short life. With the rapid development of the domestic electronic information industry, from the perspective of the development trend in recent years, solid electrolytic capacitors will gradually replace ordinary low-voltage electrolytic capacitors and will become one of the pillar products of the electronic information industry in the 21st century.
  • Doping is an effective way to improve the conductivity of polymers.
  • Polymer materials with conjugated chemical double bonds can be oxidized or reduced by adding dopants to obtain better electrochemical activity.
  • the purpose of reducing the energy band gap and reducing the migration resistance of free charges is achieved by doping, thereby significantly improving the conductivity of the conjugated polymer, and its conductivity can be increased by several to ten orders of magnitude.
  • the conjugated structure of the polymer makes the large ⁇ electrons have higher electron mobility and the degree of electron delocalization is high.
  • the current doping method usually introduces a certain dopant (such as elemental iodine, ferric chloride, etc.) into the polymer system. Due to its low electron dissociation, it can lose or partially lose electrons and be oxidized, resulting in P-type Doping; Because of its own good electron affinity, it can get or partly get electrons and be reduced, and n-type doping occurs, which increases the conductivity of the polymer.
  • a certain dopant such as elemental iodine, ferric chloride, etc.
  • the performance of capacitors is usually improved by adding external dopants.
  • the dopants and conjugated polymers have poor compatibility and poor dispersion, which hinder the further improvement of electrical conductivity.
  • the present invention provides a conductive polymer, a capacitor and a preparation method thereof.
  • the present invention provides a conductive polymer, which includes a segment obtained by polymerization of a polymer monomer, and the polymerized monomer includes a compound represented by Formula 1:
  • Y is selected from one of NH and S;
  • R 1 and R 2 are each independently selected from H or optionally substituted linear or branched alkyl, optionally substituted cycloalkyl, optionally substituted aryl Group, an optionally substituted aralkyl group, an optionally substituted alkoxy group or a hydroxyl group, and an organic group containing at least one of a carboxyl group, a sulfonic acid group and a phosphoric acid group, and at least one of R 1 and R 2 contains a carboxyl group, An organic group of at least one of a sulfonic acid group and a phosphoric acid group.
  • the alkyl group is selected from substituted or unsubstituted linear or branched C1-C18 alkyl groups
  • the cycloalkyl group is selected from substituted or unsubstituted C5-C12 cycloalkyl groups
  • the aryl group is selected from A self-substituted or unsubstituted C6-C14 aryl group
  • the aralkyl group is selected from a substituted or unsubstituted C7-C18 aralkyl group
  • the alkoxy group is selected from a substituted or unsubstituted C1-C18 alkoxy group.
  • the present invention provides a capacitor including the conductive polymer as described above.
  • the present invention provides a method for manufacturing a capacitor, including the following steps:
  • Y is selected from one of NH and S;
  • R 1 and R 2 are each independently selected from H or optionally substituted linear or branched alkyl, optionally substituted cycloalkyl, optionally substituted aryl Group, an optionally substituted aralkyl group, an optionally substituted alkoxy group or a hydroxyl group, and an organic group containing at least one of a carboxyl group, a sulfonic acid group and a phosphoric acid group, and at least one of R 1 and R 2 contains a carboxyl group, At least one organic group of sulfonic acid group and phosphoric acid group;
  • the capacitor element is impregnated in the monomer solution, and the impregnated capacitor element is taken out for drying, and then impregnated with an oxidizing agent solution for polymerization reaction, sealing and assembly to obtain a capacitor.
  • the alkyl group is selected from substituted or unsubstituted linear or branched C1-C18 alkyl groups
  • the cycloalkyl group is selected from substituted or unsubstituted C5-C12 cycloalkyl groups
  • the aryl group is selected from A substituted or unsubstituted C6-C14 aryl group
  • the aralkyl group is selected from a substituted or unsubstituted C7-C18 aralkyl group
  • the alkoxy group is selected from a substituted or unsubstituted C1-C18 alkoxy group.
  • the oxidant solution is an ethanol solution or n-butanol solution of ferric p-toluenesulfonate.
  • the temperature of the drying operation is 50°C to 150°C.
  • the temperature of the polymerization reaction is between 30°C and 200°C and the temperature is increased stepwise and then decreased stepwise, the humidity is between 0% and 60%, and the humidity is stepwise decreased to 0%, and the reaction time is 5-20 hours.
  • the impregnation operation of the oxidant solution is vacuum impregnation.
  • the vacuum degree of the vacuum impregnation operation is -0.05 to -0.10 MPa.
  • the conductive polymer provided by the present invention at least one of the 2'and 3'positions of 3,4-ethylenedioxythiophene is self-doped to introduce a carboxyl group, a sulfonic acid group or a phosphoric acid group in a chemical bond manner to obtain a polymerized monomer Compared with traditional electrolytes, carboxyl groups, sulfonic acid groups or phosphoric acid groups can effectively improve the conductive properties of conductive polymers. Conductive polymers obtained by in-situ polymerization of polymer monomers can conduct electricity through the movement of free electrons.
  • the conductive polymer has strong doping stability , The chain segment is more firmly combined, and the solid electrolytic capacitor is prepared by the polymer dispersion to effectively improve the cycle charge and discharge performance, and there will be no rapid decrease in the capacity extraction rate and rapid increase of the ESR value of the solid electrolytic capacitor due to the dedoping phenomenon Big problem.
  • An embodiment of the present invention provides a conductive polymer, which includes a segment obtained by polymerization of a polymer monomer, and the polymerized monomer includes a compound represented by Formula 1:
  • Y is selected from one of NH and S;
  • R 1 and R 2 are each independently selected from H or optionally substituted linear or branched alkyl, optionally substituted cycloalkyl, optionally substituted aryl Group, an optionally substituted aralkyl group, an optionally substituted alkoxy group or a hydroxyl group, and an organic group containing at least one of a carboxyl group, a sulfonic acid group and a phosphoric acid group, and at least one of R 1 and R 2 contains a carboxyl group, An organic group of at least one of a sulfonic acid group and a phosphoric acid group.
  • the carboxyl group, sulfonic acid group and phosphoric acid group contained in R 1 and R 2 can improve the conductivity of the polyelectrolyte to a certain extent.
  • the polyelectrolyte has a lower ESR value and is due to the carboxyl, sulfonic acid group on the conductive polymer.
  • the acid group or phosphate group is introduced by self-doping through chemical bonds, which makes the conductive polymer have stronger doping stability, and the chain segment combination is stronger.
  • the solid electrolytic capacitor can be effectively improved after the solid electrolytic capacitor is prepared by the polymer dispersion. Performance, there will be no problems with the rapid decline of the capacity extraction rate of the solid electrolytic capacitor and the rapid increase of the ESR value due to the dedoping phenomenon.
  • the optionally substituted alkyl group includes an alkyl group whose hydrogen is substituted by one or more of carboxyl group, sulfonic acid group and phosphoric acid group
  • the optionally substituted cycloalkyl group includes a carboxyl group
  • One or more of sulfonic acid group and phosphoric acid group replaces its hydrogen cycloalkyl group
  • optionally substituted aryl group includes aryl group whose hydrogen is substituted by one or more of carboxyl group, sulfonic acid group and phosphoric acid group
  • the optionally substituted aralkyl group includes an aralkyl group whose hydrogen is substituted by one or more of a carboxyl group, a sulfonic acid group and a phosphoric acid group
  • the optionally substituted alkoxy group includes a carboxyl group, a sulfonic acid group and a phosphoric acid group.
  • the alkyl group is selected from substituted or unsubstituted linear or branched C1-C18 alkyl groups
  • the cycloalkyl group is selected from substituted or unsubstituted C5-C12 cycloalkyl groups
  • the aryl group is The group is selected from substituted or unsubstituted C6-C14 aryl groups
  • the aralkyl group is selected from substituted or unsubstituted C7-C18 aralkyl groups
  • the alkoxy group is selected from substituted or unsubstituted C1-C18 alkoxy groups base.
  • Another embodiment of the present invention provides a capacitor including the conductive polymer as described above.
  • the capacitor is an aluminum electrolytic solid capacitor.
  • Another embodiment of the present invention provides a method for manufacturing a capacitor, including the following steps:
  • Y is selected from one of NH and S;
  • R 1 and R 2 are each independently selected from H or optionally substituted linear or branched alkyl, optionally substituted cycloalkyl, optionally substituted aryl Group, an optionally substituted aralkyl group, an optionally substituted alkoxy group or a hydroxyl group, and an organic group containing at least one of a carboxyl group, a sulfonic acid group and a phosphoric acid group, and at least one of R 1 and R 2 contains a carboxyl group, At least one organic group of sulfonic acid group and phosphoric acid group;
  • the capacitor element is impregnated in the monomer solution, and the impregnated capacitor element is taken out for drying, and then impregnated with an oxidizing agent solution for polymerization reaction, sealing and assembly to obtain a capacitor.
  • the capacitor element includes an anode, a separator and a cathode that are stacked and wound on each other.
  • the optionally substituted alkyl group includes an alkyl group whose hydrogen is substituted by one or more of carboxyl group, sulfonic acid group and phosphoric acid group
  • the optionally substituted cycloalkyl group includes a carboxyl group
  • One or more of sulfonic acid group and phosphoric acid group replaces its hydrogen cycloalkyl group
  • optionally substituted aryl group includes aryl group whose hydrogen is substituted by one or more of carboxyl group, sulfonic acid group and phosphoric acid group
  • the optionally substituted aralkyl group includes an aralkyl group whose hydrogen is substituted by one or more of a carboxyl group, a sulfonic acid group and a phosphoric acid group
  • the optionally substituted alkoxy group includes a carboxyl group, a sulfonic acid group and a phosphoric acid group.
  • the alkyl group is selected from substituted or unsubstituted linear or branched C1-C18 alkyl groups
  • the cycloalkyl group is selected from substituted or unsubstituted C5-C12 cycloalkyl groups
  • the aryl group is The groups are each independently selected from substituted or unsubstituted C6-C14 aryl groups
  • the aralkyl group is selected from substituted or unsubstituted C7-C18 aralkyl groups
  • the alkoxy group is selected from substituted or unsubstituted C1- C18 alkoxy.
  • the mass percentage of the polymer monomer in the monomer solution is 20%-40%.
  • the solvent in the monomer solution can be various existing organic solvents, such as ethanol.
  • the mass percentage of the oxidant in the oxidant solution is 40%-65%.
  • the oxidant solution is an ethanol solution or n-butanol solution of iron p-toluenesulfonate.
  • the oxidizing agent solution can reduce the polymerization reaction rate, appropriately extend the polymerization reaction time, facilitate the full impregnation of solid electrolytic capacitor elements, improve the conductivity and crystallinity of the conductive polymer, and will not leave other electrochemical properties of the conductive polymer Harmful impurities and easy operation.
  • the reaction process due to the low boiling point of ethanol or n-butanol solvents, the reaction process will continue to volatilize and will not remain, thereby obtaining conductive high molecular polymers with excellent electrochemical performance.
  • the temperature of the drying operation is 50°C to 150°C.
  • the temperature of the polymerization reaction is between 30°C and 200°C, and the temperature is increased stepwise and then decreased stepwise.
  • the humidity is between 0% and 60% and the humidity is stepwise decreased to 0%, and the reaction time is between 5°C and 200°C. 20h.
  • the temperature of the drying operation is between 60°C and 100°C
  • the temperature of the polymerization reaction is between 50°C and 130°C
  • the temperature is increased stepwise and then decreased stepwise
  • the humidity is 0-40°C. Decrease the humidity stepwise to 0% between %
  • the reaction time is 7-13h.
  • the stepped temperature rise and fall and humidity reduction can effectively promote the stable progress of the polymerization reaction and remove volatile solvents and moisture.
  • the impregnation operation of the oxidant solution is vacuum impregnation.
  • the vacuum degree of the vacuum impregnation operation is -0.05 to -0.10 MPa.
  • the vacuum impregnation operation can promote the oxidant solution to penetrate more into the capacitor element, fully mix the oxidant and the polymer monomer, promote the subsequent polymerization reaction, and avoid mixing of air during the impregnation process.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • S1, 3,4-ethylenedioxythiophene-2'-methanesulfonic acid is used as the polymer monomer
  • ethanol is used as the solvent to prepare a 25% monomer solution
  • the capacitor element is used to impregnate the monomer solution 2min, take out the capacitor element and dry it in an oven at 80°C for 30min, then cool to room temperature;
  • the element is vacuum impregnated with a 55% concentration of ferric p-toluenesulfonate ethanol oxidant solution, the vacuum degree is -0.085MPa, slowly put the capacitor element into the oxidant solution, and keep the temperature at 20-25°C Between, the time is maintained for 5 minutes;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • the element is vacuum impregnated with a 60% concentration of ferric p-toluenesulfonate ethanol oxidizer solution, the vacuum degree is -0.09MPa, slowly put the capacitor element into the oxidizer solution, and keep the temperature at 20-25°C Between, the time is maintained for 5 minutes;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • S1, 3,4-ethylenedioxythiophene-2'-acetic acid is used as the polymer monomer, and ethanol is used as the solvent to prepare a 26% monomer solution.
  • the capacitor element is used to impregnate the monomer solution for 2 minutes, Take out the capacitor element and dry it in an oven at 100°C for 30 minutes, then cool to room temperature;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • S1, 3,4-ethylenedioxythiophene-2'-methoxymethanesulfonic acid is used as the polymer monomer, and ethanol is used as the solvent to prepare a 25% monomer solution, and the capacitor element is used for impregnation
  • the monomer solution is 2min, and the capacitor element is taken out and dried in an oven at 150°C for 30min, and then cooled to room temperature;
  • the element is vacuum impregnated with a 55% concentration of ferric p-toluenesulfonate ethanol oxidant solution, the vacuum degree is -0.085MPa, slowly put the capacitor element into the oxidant solution, and keep the temperature at 20-25°C Between, the time is maintained for 5 minutes;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This embodiment is used to illustrate the polymer electrolyte, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps:
  • S1, 3,4-ethylenedioxythiophene-2'-methyl phosphoric acid is used as the polymer monomer
  • ethanol is used as the solvent to prepare a 27% monomer solution
  • the capacitor element is used to impregnate the monomer solution for 2 minutes , Take out the capacitor element and dry it in an oven at 120°C for 30 minutes, then cool it to room temperature;
  • the element after the above steps is vacuum impregnated with a 60% concentration of ferric p-toluenesulfonate ethanol oxidant solution, the vacuum degree is -0.08MPa, slowly put the capacitor element into the oxidant solution, and keep the temperature at 20-25°C Between, the time is maintained for 5 minutes;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • This comparative example is used to compare and illustrate the conductive polymer, capacitor and preparation method thereof disclosed in the present invention, including the following operation steps.
  • S1, 3,4-ethylenedioxythiophene is used as the polymer monomer, and ethanol is used as the solvent to prepare a 27% monomer solution of the polymer monomer, and the capacitor element is used to impregnate the solution for about 2 minutes in an oven at 100°C Dry for 30 minutes, then cool to room temperature;
  • the capacitor is sealed and assembled into a solid electrolytic capacitor.
  • test method refers to the measurement of conventional solid electrolytic capacitors, which will not be repeated here.
  • the solid electrolytic capacitor was charged for 3 seconds and then discharged for 3 seconds. After repeated cycles of 1000 times, the electrostatic capacity, loss value and equivalent series resistance of the solid electrolytic capacitor were tested again.
  • the solid electrolytic capacitor prepared by the conductive polymer provided by the present invention has a lower ESR value, and the capacity decay rate is lower after cyclic charge and discharge, and the largest decay rate is only
  • the capacity decay rate of the solid electrolytic capacitor prepared by using conventional monomers in Comparative Example 1 is relatively large after cyclic charging and discharging, which is 7.3%, indicating that the conductive polymer of the present invention undergoes cyclic charging and discharging. After that, there will be basically no dedoping phenomenon, and the stability of the conductive polymer is excellent, thereby ensuring the stability of the performance of the solid electrolytic capacitor and greatly improving the service life of the solid electrolytic capacitor.

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Abstract

为克服现有固态电容器中导电聚合物存在电导率差，以及现有电解质添加掺杂剂的方式存在脱掺杂的问题，本发明提供了一种导电聚合物，包括由聚合物单体聚合得到的链段，所述聚合单体包括通式（I）所示的化合物：其中，Y选自NH、S中的一种；R1、R2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R1和R2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团。同时，本发明还公开了包括上述导电聚合物的电容器及其制备方法。本发明提供的导电聚合物具有较低的ESR值，同时电性能稳定。

Description

一种导电聚合物、电容器及其制备方法 技术领域
本发明属于电容器技术领域，具体涉及一种导电聚合物、电容器及其制备方法。
背景技术
与普通电解电容器相比，固体电解电容器采用电导率高、热稳定性好的固体导电材料作为电解质，不但具有普通电解电容器所有特性，而且具有可靠性好、使用寿命长、高频低阻抗、耐特大纹波电流等特性，并可以克服液态电解电容器容易漏液、寿命短的弊端。随着国内电子信息产业的飞速发展，从近几年的发展趋势来看，固体电解电容器将逐步替代普通低压电解电容器，并将成为21世纪电子信息产业的支柱产品之一。
随着人们对固态电解电容器性能要求的提高，进一步提高导电高分子聚合物电导率，从而降低电容器ESR值成为研究者共同追求的目标。掺杂是提高聚合物导电性的一种有效途径，具有共轭化学双键的高分子材料可以通过加入掺杂剂被氧化或被还原以获得更好的电化学活性。通过掺杂达到减小能带隙和降低自由电荷的迁移阻力的目的，从而显著提高共轭高分子的导电性，其电导率可提高几到十几个数量级。聚合物的共轭结构，使得大π电子具有较高的电子流动性，电子离域程度高。目前的掺杂方法通常是将某种掺杂剂(如单质碘、氯化铁等)引入聚合物体系中，由于其电子离解性较低，可失去或部分失去电子而被氧化，发生P型掺杂；又因为其自身良好的电子亲和力，可得到或部分得到电子而被还原，发生n型掺杂，致使聚合物的电导率提高。例如，现有技术中大多采用聚苯乙烯磺酸、对甲基苯磺酸等掺杂剂对导电高分子材料进行掺杂，从而提高电导率。
目前通常采用通过添加外掺杂剂的方式来提升电容器性能，但是，掺杂剂与共轭高分子存在相容性差、分散性不好等问题，阻碍了电导率的进一步提高。并且，尤为重要的是，通过目前常用的掺杂剂掺杂后的聚合物分散体用于固态电解电容器之后，在进行充放电过程中，常常会出现脱掺杂现象，进而使得固 态电解电容器容量引出率会迅速下降，ESR值迅速增大，导致固态电解电容器性能迅速劣化而失效。
发明内容
针对现有固态电容器中导电聚合物分散体存在电导率差，以及现有电解质添加掺杂剂的方式存在脱掺杂的问题，本发明提供了一种导电聚合物、电容器及其制备方法。
本发明解决上述技术问题所采用的技术方案如下：
一方面，本发明提供了一种导电聚合物，包括由聚合物单体聚合得到的链段，所述聚合单体包括通式一所示的化合物：
Figure PCTCN2020089098-appb-000001
其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团。
可选的，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基选自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述烷氧基选自取代或未取代的C1‐C18烷氧基。
另一方面，本发明提供了一种电容器，包括如上所述的导电聚合物。
另一方面，本发明提供了一种电容器的制备方法，包括如下操作步骤：
获取单体溶液，所述单体溶液中包括通式一所示的化合物：
Figure PCTCN2020089098-appb-000002
其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团；
将电容器素子含浸于所述单体溶液中，取出含浸后的电容器素子进行烘干，再含浸氧化剂溶液，进行聚合反应，封口组立，得到电容器。
可选的，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述烷氧基选自取代或未取代的C1‐C18烷氧基。
可选的，所述氧化剂溶液为对甲基苯磺酸铁的乙醇溶液或正丁醇溶液。
可选的，所述烘干操作的温度为50℃～150℃。
可选的，所述聚合反应的温度在30℃～200℃之间先阶梯式升温后阶梯式降温，湿度在0～60％之间阶梯式降低湿度至0％，反应时间为5～20h。
可选的，所述氧化剂溶液的含浸操作为真空含浸。
可选的，所述真空含浸操作的真空度为‐0.05～‐0.10MPa。
根据本发明提供的导电聚合物，在3,4‐乙撑二氧噻吩的2’位和3’位的至少一处以化学键的方式自掺杂引入羧基、磺酸基或磷酸基，得到聚合单体，聚合物单体经原位聚合反应得到的导电聚合物相比于传统电解质来说，羧基、磺酸基或磷酸基可有效提高导电聚合物的导电性能，其通过自由电子移动而导电，可有效提高电荷在界面迁移效率，从而提高电导率，且由于导电聚合物上的羧基、磺酸基或磷酸基是通过化学键自掺杂引入的，使得导电聚合物具有较强的掺杂稳定性，链段结合更加牢固，通过该聚合物分散体制备固态电解电容器后可有效改善循环充放电性能，不会出现因为脱掺杂现象而导致固态电解电容器 的容量引出率迅速下降及ESR值迅速增大的问题。
具体实施方式
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明一实施例提供了一种导电聚合物，包括由聚合物单体聚合得到的链段，所述聚合单体包括通式一所示的化合物：
Figure PCTCN2020089098-appb-000003
其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团。
通过R 1和R 2中含有的羧基、磺酸基和磷酸基能够在一定程度上提高聚合电解质的电导率，所述聚合电解质具有较低的ESR值，且由于导电聚合物上的羧基、磺酸基或磷酸基是通过化学键自掺杂引入的，使得导电聚合物具有较强的掺杂稳定性，链段结合更加牢固，通过该聚合物分散体制备固态电解电容器后可有效改善循环充放电性能，不会出现因为脱掺杂现象而导致固态电解电容器的容量引出率迅速下降及ESR值迅速增大的问题。
需要说明的是，上述描述中，任选取代的烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的烷基，任选取代的环烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的环烷基，任选取代的芳基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的芳基，任选取代的芳烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的芳烷基，任选取代的烷氧基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的烷氧基。
在一些实施例中，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基选自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述烷氧基选自取代或未取代的C1‐C18烷氧基。
本发明的另一实施例提供了一种电容器，包括如上所述的导电聚合物。
所述电容器为铝电解固态电容器。
本发明的另一实施例提供了一种电容器的制备方法，包括如下操作步骤：
获取单体溶液，所述单体溶液中包括通式一所示的化合物：
Figure PCTCN2020089098-appb-000004
其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团；
将电容器素子含浸于所述单体溶液中，取出含浸后的电容器素子进行烘干，再含浸氧化剂溶液，进行聚合反应，封口组立，得到电容器。
所述电容器素子包括相互层叠卷绕的阳极、隔膜和阴极。
需要说明的是，上述描述中，任选取代的烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的烷基，任选取代的环烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的环烷基，任选取代的芳基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的芳基，任选取代的芳烷基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的芳烷基，任选取代的烷氧基包括由羧基、磺酸基和磷酸基中的一种或多种取代其氢的烷氧基。
在一些实施例中，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基各自独立地选自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述 烷氧基选自取代或未取代的C1‐C18烷氧基。
在一些实施例中，所述单体溶液中聚合物单体的质量百分含量为20％～40％。
所述单体溶液中溶剂可采用现有的各种有机溶剂，如乙醇。
在一些实施例中，所述氧化剂溶液中氧化剂的质量百分含量为40％～65％。
在一些实施例中，所述氧化剂溶液为对甲基苯磺酸铁的乙醇溶液或正丁醇溶液。
所述氧化剂溶液可降低聚合反应速率，适当延长聚合反应时间，有利于固态电解电容器素子充分含浸，提高导电聚合物的导电性和结晶性，且不会残余其它对导电高分子聚合物电化学性能有害的杂质，同时操作简便。且乙醇或正丁醇类溶剂由于沸点低，反应过程会不断挥发，不会残留，从而得到电化学性能优良的导电高分子聚合物。
在一些实施例中，所述烘干操作的温度为50℃～150℃。
在一些实施例中，所述聚合反应的温度在30℃～200℃之间先阶梯式升温后阶梯式降温，湿度在0～60％之间阶梯式降低湿度至0％，反应时间为5～20h。
在一些优选的实施例中，所述烘干操作的温度为60℃～100℃，所述聚合反应的温度在50℃～130℃之间先阶梯式升温后阶梯式降温，湿度在0～40％之间阶梯式降低湿度至0％，反应时间为7～13h。
通过阶梯式的升降温和湿度降低，能够有效促进聚合反应的稳定进行，去除其中的挥发性溶剂和水分。
在一些实施例中，所述氧化剂溶液的含浸操作为真空含浸。
在更优选的实施例中所述真空含浸操作的真空度为‐0.05～‐0.10MPa。
通过真空含浸操作，能够促进氧化剂溶液更多地渗透入电容器素子中，使氧化剂与聚合物单体充分混合，促进后续聚合反应，同时避免在含浸过程中混入空气。
以下通过实施例对本发明进行进一步的说明。
实施例1
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’‐甲磺酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成25％的单体溶液，使用电容器素子含浸单体溶液2min，取出 电容器素子于80℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸55％浓度的对甲基苯磺酸铁乙醇氧化剂溶液，真空度为‐0.085MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度50℃，湿度30％条件下，反应2h；调节温度至70℃，湿度至20％，反应2h；调节温度至150℃，湿度至0％，反应1h；调节温度至110℃，湿度至0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例2
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’,3’‐二甲磺酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成27％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于90℃烘箱内干燥30min，后冷却至常温；
S2、述步骤处理之后的素子真空含浸60％浓度的对甲基苯磺酸铁乙醇氧化剂溶液，真空度为‐0.09MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度40℃，湿度40％条件下，反应2h；调节温度至60℃，湿度至20％，反应2h；调节温度至130℃，湿度至0％，反应1h；调节温度至105℃，湿度至0％，反应4h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例3
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’‐乙酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成26％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于100℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸50％浓度的对甲基苯磺酸铁正丁醇氧化剂溶液，真空度为‐0.085MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度50℃，湿度35％条件下，反应2h；调节温度至60℃，湿度至25％，反应3h；调节温度至140℃，湿度至0％，反应2h；调节温度至105℃，湿度至0％，反应4h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例4
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’,3’‐丁二酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成26％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于130℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸55％浓度的对甲基苯磺酸铁正丁醇氧化剂溶液，真空度为‐0.09MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度60℃，湿度30％条件下，反应2h；调节温度至100℃，湿度至0％，反应2h；调节温度至150℃，湿度至0％，反应2h；调节温度至110℃，湿度至0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例5
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’–甲氧基甲磺酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成25％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于150℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸55％浓度的对甲基苯磺酸铁乙醇氧 化剂溶液，真空度为‐0.085MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度40℃，湿度40％条件下，反应1h；调节温度至80℃，湿度至20％，反应2h；调节温度至130℃，湿度至0％，反应2h；调节温度至100℃，湿度至0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例6
本实施例用于说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’,3’–二甲氧基甲磺酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成28％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于120℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸50％浓度的对甲基苯磺酸铁正丁醇氧化剂溶液，真空度为‐0.09MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度50℃，湿度30％条件下，反应2h；调节温度至70℃，湿度至20％，反应2h；调节温度至140℃，湿度至0％，反应2h；调节温度至105℃，湿度至0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
实施例7
本实施例用于说明本发明公开的聚合物电解质、电容器及其制备方法，包括以下操作步骤：
S1、采用3,4‐乙撑二氧噻吩‐2’‐甲磷酸作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成27％的单体溶液，使用电容器素子含浸单体溶液2min，取出电容器素子于120℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸60％浓度的对甲基苯磺酸铁乙醇氧化剂溶液，真空度为‐0.08MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度 在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度60℃，湿度30％条件下，反应2h；调节温度至90℃，湿度至20％，反应2h；调节温度至150℃，湿度至0％，反应1h；调节温度至110℃，湿度至0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
对比例1
本对比例用于对比说明本发明公开的导电聚合物、电容器及其制备方法，包括以下操作步骤。
S1、采用3,4‐乙撑二氧噻吩作为聚合物单体，采用乙醇为溶剂将聚合物单体配制成27％的单体溶液，使用电容器素子含浸该溶液2min左右，于100℃烘箱内干燥30min，后冷却至常温；
S2、上述步骤处理之后的素子真空含浸55％浓度的对甲基苯磺酸铁正丁醇氧化剂溶液，真空度为‐0.09MPa，将电容器素子缓慢放入氧化剂溶液中，保持温度在20～25℃之间，时间维持5min；
S3、含浸完毕后，将电容器素子移出，放入恒温恒湿箱进行聚合反应，在温度50℃，湿度30％条件下，反应2h；调节温度至80℃，湿度至20％，反应2h；调节温度至150℃，湿度至0％，反应2h；调节温度至105℃，湿至度0％，反应3h；
S4、聚合反应完毕，电容器封口组立装配成固态电解电容器。
性能测试
对上述实施例1～7和对比例1制备得到的固态电解电容器进行如下性能测试：
使用自动电子零件分析仪对电容器的静电容量、损耗值和等效串联电阻进行测试，测试方式参考常规的固态电解电容器的测量，在此不累述。
然后在1.15倍额定电压条件下，对固态电解电容器进行3秒充电后3秒放电，反复循环1000次后，再次对固态电解电容器的静电容量、损耗值和等效串联电阻进行测试。
测试结果如表1所示。
得到的测试结果填入表1。
表1固体铝电解电容器各项性能测试结果(16V470μF芯包)
Figure PCTCN2020089098-appb-000005
从表1的测试结果可以看出，通过本发明提供的导电聚合物制备得到的固态电解电容器具有较低的ESR值，在经过循环充放电后容量衰减率均较低，衰减率最大的也仅为‐1.1％；而对比例1中采用常规的单体制备得到的固态电解电容器在经过循环充放电后容量衰减率较大，为‐7.3％，说明本发明的导电聚合物在经过循环充放电后基本不会出现脱掺杂的现象，导电聚合物的稳定性极佳，从而确保了固态电解电容器性能的稳定性，极大地提升了固态电解电容器的使用寿命。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种导电聚合物，其特征在于，包括由聚合物单体聚合得到的链段，所述聚合单体包括通式一所示的化合物：
    Figure PCTCN2020089098-appb-100001
    其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团。
  2. 根据权利要求1所述的导电聚合物，其特征在于，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基选自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述烷氧基选自取代或未取代的C1‐C18烷氧基。
  3. 一种电容器，其特征在于，包括权利要求1或2所述的导电聚合物。
  4. 一种电容器的制备方法，其特征在于，包括如下操作步骤：
    获取单体溶液，所述单体溶液中包括通式一所示的化合物：
    Figure PCTCN2020089098-appb-100002
    Figure PCTCN2020089098-appb-100003
    其中，Y选自NH、S中的一种；R 1、R 2各自独立的选自H或任选取代的直链或支链烷基、任选取代的环烷基、任选取代的芳基、任选取代的芳烷基、任选取代的烷氧基或羟基以及含有羧基、磺酸基和磷酸基中至少一种的有机基团，并且R 1和R 2至少一个为含有羧基、磺酸基和磷酸基中至少一种的有机基团；
    将电容器素子含浸于所述单体溶液中，取出含浸后的电容器素子进行烘干，再含浸氧化剂溶液，进行聚合反应，封口组立，得到电容器。
  5. 根据权利要求4所述的电容器的制备方法，其特征在于，所述烷基选自取代或未取代的直链或支链C1‐C18烷基，所述环烷基选自取代或未取代的C5‐C12环烷基，所述芳基选自取代或未取代的C6‐C14芳基，所述芳烷基选自取代或未取代的C7‐C18芳烷基，所述烷氧基选自取代或未取代的C1‐C18烷氧基。
  6. 根据权利要求4所述的电容器的制备方法，其特征在于，所述氧化剂溶液为对甲基苯磺酸铁的乙醇溶液或正丁醇溶液。
  7. 根据权利要求4所述的电容器的制备方法，其特征在于，所述烘干操作的温度为50℃～150℃。
  8. 根据权利要求4所述的电容器的制备方法，其特征在于，所述聚合反应的温度在30℃～200℃之间先阶梯式升温后阶梯式降温，湿度在0～60％之间阶梯式降低湿度至0％，反应时间为5～20h。
  9. 根据权利要求4所述的电容器的制备方法，其特征在于，所述氧化剂溶液的含浸操作为真空含浸。
  10. 根据权利要求9所述的电容器的制备方法，其特征在于，所述真空含浸操作的真空度为‐0.05～‐0.10MPa。
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JP2017105982A (ja) * 2015-12-04 2017-06-15 東ソー株式会社 帯電防止薄膜、及び帯電防止用水溶液
CN109716466A (zh) * 2016-09-15 2019-05-03 阿维科斯公司 具有改进的泄露电流的固体电解电容器
CN111048319A (zh) * 2019-11-13 2020-04-21 株洲宏达电子股份有限公司 一种水相电化学聚合噻吩制作片式钽电容器及其制作方法

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