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WO2017143737A1 - 一种铝电解质电容器及其制备方法 - Google Patents

一种铝电解质电容器及其制备方法 Download PDF

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Publication number
WO2017143737A1
WO2017143737A1 PCT/CN2016/094922 CN2016094922W WO2017143737A1 WO 2017143737 A1 WO2017143737 A1 WO 2017143737A1 CN 2016094922 W CN2016094922 W CN 2016094922W WO 2017143737 A1 WO2017143737 A1 WO 2017143737A1
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WIPO (PCT)
Prior art keywords
electrolytic capacitor
aluminum electrolytic
dispersion
formula
capacitor according
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PCT/CN2016/094922
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English (en)
French (fr)
Inventor
赵大成
李付亚
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深圳新宙邦科技股份有限公司
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Publication of WO2017143737A1 publication Critical patent/WO2017143737A1/zh

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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
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—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
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • 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
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • 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 present application relates to the field of capacitors, and in particular to an aluminum electrolytic capacitor and a method of manufacturing the same.
  • the conductive polymer is a kind of polymer compound having a conjugated ⁇ bond structure, which is chemically or electrochemically doped to form an anion or a cation to form a conductive special polymer material, including polyacetylene, polythiophene, polypyrrole. , polyaniline, polyparaphenylene, polycarbazole and polyfluorene.
  • conductive polymers have both the photoelectric properties of metal and semiconductor materials, good polymer stability and mechanical properties, relatively light weight, and ease of processing.
  • the most successful conductive polymers currently used in the industrial field are polyaniline and polythiophene, especially poly(3,4-ethylenedioxythiophene) (PEDOT) among polythiophene derivatives, but also because of its high conductivity, Good environmental stability, transparency in doped state, etc., and widely used in electronic devices such as organic electro-display, organic solar cells and supercapacitors.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • the Chinese invention patent No. 200680033112.0 discloses a method for preparing an electrolytic capacitor, the method comprising at least the following steps: a) subjecting the porous electrode body (2) of the electrode material to anodization to form a dielectric covering the surface of the electrode material.
  • the conductive polymer particles B) in the dispersion A) have an average particle diameter of from 1 to 100 nm.
  • the applied conductive particles have an average particle diameter of 1-100 nm and an anodization voltage of more than 30V. It has been found through testing that the electrolytic capacitor of the above invention still has problems in that the capacity and loss, the equivalent series resistance, and the leakage performance cannot be balanced.
  • the technical problem to be solved by the present invention is to provide an aluminum electrolytic capacitor which can control a suitable molecular weight, which is easy to discharge, low in loss, low in equivalent series resistance, and low in leakage, and further provides a method for preparing the above aluminum electrolytic capacitor.
  • the technical solution adopted by the present invention is:
  • An aluminum electrolytic capacitor having an oxidation voltage of an anode of the aluminum electrolytic capacitor of more than 30 V, comprising a dispersion comprising a conductive polymer and a dispersant, the conductive polymer having an average particle diameter of 10 to 30 nm.
  • the present invention also provides a method of preparing an aluminum electrolytic capacitor, the dispersion is applied to an electrode of the above-described aluminum electrolytic capacitor, and then the dispersant is partially or completely removed, or the dispersant is cured.
  • the number of removals or curings is one or more times.
  • the obtained aluminum electrolytic capacitor has the advantages of low loss, low equivalent series resistance, and low leakage.
  • the most critical idea of the present invention is that, by controlling the average particle diameter of the conductive polymer to be 10-30 nm under the condition that the anodization voltage is greater than 30 V, the technical effect of easy discharge is achieved.
  • the present invention provides an aluminum electrolytic capacitor having an anodic oxidation voltage of more than 30 V, comprising a dispersion comprising a conductive polymer and a dispersant, the conductive polymer having an average particle diameter of 10 30nm.
  • the present invention also provides a method of preparing an aluminum electrolytic capacitor, the dispersion is applied to an electrode of the above-described aluminum electrolytic capacitor, and then the dispersant is partially or completely removed, or the dispersant is cured.
  • the number of removals or curings is one or more times.
  • the particle size is smaller, but the stability and electrical conductivity are deteriorated. Therefore, when the particle diameter is 1-10 nm, the particle diameter is too small, and the conductivity of the dispersion is low, and the prepared capacitor is obtained.
  • the equivalent series resistance will become larger; when the molecular weight is large, the particle size is large, the stability is good, and the conductivity is superior, but the molecular weight is too large, and the particle size is too large, which is unfavorable for entering the pores of the porous anode;
  • the capacitor obtained by the preparation has a low capacity and high loss. Therefore, the prior art electrolytic capacitor has a problem that the capacity, the loss performance, the equivalent series resistance, and the electrical conductivity (such as leakage performance) cannot be balanced.
  • the particle size of the conductive particles is controlled to be between 10-30 nm, and the PEDOT/PSS dispersion is sheared, and the particle size and aggregation after homogenization.
  • the molecular weight of styrene sulfonic acid (pss) is closely related; considering the stability, conductivity and particle size of the dispersion, and through long-term experiments, the oxidation voltage at the anode is greater than 30V, and the average particle size of the conductive polymer is controlled. It is 10-30nm. At this time, the combination of pore size and particle size can achieve the technical effect of high capacity.
  • the obtained aluminum electrolytic capacitor has the advantages of low loss, low equivalent series resistance, and low leakage.
  • the obtained aluminum electrolytic capacitor has the advantages of low loss, low equivalent series resistance, and low leakage.
  • the conductive polymer comprises a polythiophene derivative
  • the polythiophene derivative comprises a repeating unit having the composition of the following formula I and/or formula II, wherein the formula of the formula I is:
  • A is an optionally substituted alkylene group having 1 to 5 carbon atoms
  • R is an optionally substituted direct bond having 5 to 12 carbon atoms or A branched cycloalkyl group, an optionally substituted straight or branched aryl group having 6 to 14 carbon atoms, an optionally substituted linear or branched aralkyl group having 7 to 18 carbon atoms, optionally substituted A linear or branched hydroxyalkyl group having a carbon number of 1 to 4 or a hydroxyl group
  • X is an integer of 0-8.
  • A binds to several A groups, these groups may be the same or different.
  • the polythiophene derivative of the present invention may be a repeating unit having a composition of the formula I, a repeating unit having a composition of the formula II, or a repeating unit having a composition of the formula I and the formula II.
  • the polythiophene derivative may be an optionally substituted polythiophene, and preferably the above-mentioned repeating unit having a composition of the following formula I and/or formula II.
  • the polythiophene derivative of the above structure can be better matched with the pore size of the anode to further improve the ease of discharge.
  • the conductive polymer further includes at least one of a polypyrrole derivative and a polyaniline derivative.
  • the dispersion further comprises a polymeric anion.
  • the polymeric anion is a polymeric carboxylic acid anion or a polymeric sulfonate anion. More preferably, the polymeric anion is a polystyrene sulfonate anion having a molecular weight of from 2,000 to 500,000.
  • a polymeric anion is added to the dispersion, and the polyanion can be used as a composite ion, which is complexed with polythiophene and then dispersed in water.
  • the polyanion can also act as a dopant to control the molecular weight of the polystyrene sulfonate anion to 2000- 500000, the polythiophene can be better dispersed in water.
  • the polystyrenesulfonate anion has a molecular weight of 10,000 to 200,000.
  • the dispersing agent is an organic solvent and/or water.
  • the dispersion further includes at least one of a crosslinking agent, a surfactant, and an additive selected from the group consisting of an ether, a lactone, an amide group, a lactam group, a sulfone, a sulfoxide, a sugar, At least one of a sugar derivative, a sugar alcohol, a furan derivative, a glycol, and a polyol.
  • a crosslinking agent selected from the group consisting of an ether, a lactone, an amide group, a lactam group, a sulfone, a sulfoxide, a sugar, At least one of a sugar derivative, a sugar alcohol, a furan derivative, a glycol, and a polyol.
  • crosslinking agent and the surfactant may be those commonly used in the prior art as crosslinking agents and surfactants.
  • the addition of the crosslinking agent, the surfactant and the additive respectively have an effect of effectively crosslinking and lowering the surface tension.
  • the dispersion has a pH of 1.5-7, and the dispersion has a viscosity of not more than 500 cps at 20 °C.
  • the pH and viscosity of the dispersion can be controlled as described above. More preferably, the pH of the dispersion is 2 to 5, and the viscosity can be tested at 60 rpm.
  • the pH in the dispersion can be adjusted by adding an acid or a base; the step of "applying the dispersion and then partially or completely removing the dispersant or curing the dispersant" can be carried out once or repeatedly. More than two times.
  • the design of the synthesis of the dispersion of the present invention and the screening of the composition of the dispersion raw material can sufficiently take into consideration the stability, conductivity and particle diameter of the dispersion to obtain good properties (easier capacity, low loss, etc.) Low series resistance and low leakage).
  • An aluminum electrolytic capacitor of the embodiment wherein an anode of the aluminum electrolytic capacitor has an oxidation voltage of 30 V, and includes a dispersion comprising a conductive polymer, a dispersant, and a polymeric anion, and further comprising an additive, wherein the additive is A mixture of an ether, a lactone, an amide group, a furan derivative, and a polyol.
  • the dispersion had a pH of 1.5 and the dispersion had a viscosity of 500 cps at 20 °C.
  • the conductive polymer had an average particle diameter of 10 nm.
  • the conductive polymer includes a polythiophene derivative, and further includes a polypyrrole derivative.
  • the polymeric anion is a polystyrene sulfonate anion, the polystyrene sulfonate anion has a molecular weight of 2000, and the dispersing agent is water.
  • the polythiophene derivative includes a repeating unit having the composition of the following formula I, and the structural formula of the formula I is:
  • A is an optionally substituted alkylene group having 1 carbon atom
  • R is an optionally substituted straight or branched cycloalkyl group having 5 carbon atoms, optionally substituted a linear aryl group having 6 carbon atoms, an optionally substituted linear aralkyl group having 7 carbon atoms, an optionally substituted linear hydroxyalkyl group having 1 carbon atom or a hydroxyl group
  • X is 0.
  • An aluminum electrolytic capacitor of the embodiment wherein an anode of the aluminum electrolytic capacitor has an oxidation voltage of 50 V, and comprises a dispersion comprising a conductive polymer, a dispersant, and a polymeric anion, and further comprising an additive, wherein the additive is ether.
  • the pH of the dispersion was 7, and the viscosity of the dispersion at 20 ° C was 400 cps.
  • the conductive polymer had an average particle diameter of 30 nm.
  • the conductive polymer includes a polythiophene derivative, and further includes a polypyrrole derivative and a polyaniline derivative.
  • the polymeric anion is a polystyrene sulfonate anion, the polystyrene sulfonate anion has a molecular weight of 500,000, and the dispersing agent is an organic solvent.
  • the polythiophene derivative includes a repeating unit having the composition of the following formula II, and the structural formula of the formula II is:
  • A is an optionally substituted alkylene group having 5 carbon atoms
  • R is an optionally substituted branched cycloalkyl group having 12 carbon atoms, optionally substituted carbon atoms Is a branched aryl group of 14, an optionally substituted branched aralkyl group having 18 carbon atoms, an optionally substituted branched hydroxyalkyl group having 4 carbon atoms or a hydroxyl group
  • X is 8.
  • An aluminum electrolytic capacitor of the embodiment wherein an anode of the aluminum electrolytic capacitor has an oxidation voltage of 60 V, comprising a dispersion comprising a conductive polymer, a dispersant, and a polymeric anion, further comprising an additive, wherein the additive is Amide group.
  • the dispersion had a pH of 4 and the dispersion had a viscosity of 200 cps at 20 °C.
  • the conductive polymer had an average particle diameter of 20 nm.
  • the conductive polymer includes a polythiophene derivative, and further includes a polyaniline derivative.
  • the polymeric anion is a polystyrene sulfonate anion, the polystyrene sulfonate anion has a molecular weight of 300,000, and the dispersing agent is water.
  • the polythiophene derivative includes a repeating unit having the composition of the following formula I and formula II, wherein the formula of the formula I is:
  • A is an optionally substituted alkylene group having 2 carbon atoms; and R is an optionally substituted linear cycloalkyl group having 8 carbon atoms.
  • a substituted linear aryl group having 10 carbon atoms, an optionally substituted linear aralkyl group having 10 carbon atoms, and optionally substituted carbon atoms Is a branched hydroxyalkyl group or a hydroxyl group of 3;
  • X is 4.
  • polystyrenesulfonic acid (molecular weight 25000) was added to 2000 g of deionized water, stirred for 30 minutes, then 50 g of 35% aqueous sodium persulfate solution, 1% aqueous solution of ferric sulfate 14.4 g and 9.1 g of 3,4-dioxane
  • the oxythiophene was uniformly added to the above aqueous solution and stirred for 24 hours.
  • 200 g of a cationic resin was added to the reaction system, and 200 g of an anion resin was stirred for 2 hours, and the resin was filtered off to obtain a poly(3,4-dialkoxythiophene) polyanion dispersion.
  • Table 1 is a performance test table in which the cores of the four specifications contain the dispersion B.
  • Example 1 100 g of the poly(3,4-dialkoxythiophene) polyanion dispersion of Example 1, 5 g of dimethyl sulfoxide, 5 g of polyethylene glycol 400, 0.5 g of 3-glycidoxy trimethoxysilane (Silquest A-187), 2 g of sorbitol, 0.5 g of Dynol 604 (Air product) were mixed in a glass beaker with a magnetic stirrer to form a dispersion C.
  • Table 2 is a performance test table in which the cores of the four specifications contain the dispersion C.
  • Example 1 100 g of the poly(3,4-dialkoxythiophene) polyanion dispersion of Example 1, 5 g of dimethyl sulfoxide, 5 g of polyethylene glycol 200, 0.5 g of 3-glycidoxytrimethoxysilane (Silquest A-187), 2 g xylitol, 0.5 g Dynol 604 (Air product) were mixed in a glass beaker with a magnetic stirrer to form a dispersion D.
  • the cores of the four specifications were separately contained in Dispersion D, and then dried at 120 ° C and tested for their properties.
  • Table 3 is a performance test table in which the cores of the four specifications contain the dispersion D.
  • the aluminum electrolytic capacitor of the present application has a capacitance of 10-220 ⁇ F, a DF value of 1.4-1.6%, and an equivalent series resistance of 6-18 m ⁇ , and has an easy discharge, low loss, and low equivalent series resistance. And the advantage of low leakage.
  • the aluminum electrolytic capacitor provided by the present application has the advantages of easy discharge, low loss, low equivalent series resistance, and low leakage.

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Abstract

一种铝电解质电容器及其制备方法，所述铝电解质电容器的阳极的氧化电压大于30V，包括分散体，所述分散体包括导电聚合物和分散剂，所述导电聚合物的平均粒径为10-30nm。该铝电解质电容器具有出容容易、损耗低、等效串联电阻低以及漏电低的优点。

Description

一种铝电解质电容器及其制备方法 技术领域
本申请涉及电容器领域，特别是涉及一种铝电解质电容器及其制备方法。
背景技术
导电聚合物是一类具有共轭π键结构的高分子化合物，经过化学或电化学掺杂对阴离子或对阳离子后形成的具有导电性的特殊高分子材料，包括聚乙炔、聚噻吩、聚吡咯、聚苯胺、聚对苯、聚咔唑和聚芴等。导电聚合物的突出优点是既具有金属和半导体材料的光电特性，又具有聚合物良好的稳定性和力学性能，质量相对较轻，并且容易加工。目前工业领域应用最成功的导电聚合物是聚苯胺和聚噻吩，特别是聚噻吩衍生物之中的聚(3，4-乙撑二氧噻吩)(PEDOT)，更是因其高电导率、良好的环境稳定性、掺杂状态时透明等优点，而在有机电致显示、有机太阳能电池和超级电容器等电子器件中得到广泛商业应用。
自导电高分子发现以来，无论是电化学方法还是化学方法制备得到的产物一般都是难溶性的导电聚合物粉末，难以加工，因此极大的限制了其应用。直到上世纪80年代拜耳公司在3，4-乙撑二氧噻吩(EDOT)的化学氧化聚合过程中，引入聚对苯乙烯磺酸(PSS)作为电荷平衡掺杂剂，制备出聚(3，4-乙撑二氧噻吩)/聚对苯乙烯磺酸(PEDOT/PSS)，其具有优良的水分散性能、涂布成膜性能、高导电性能、光学透明性、环境稳定性等，目前已应用于超级电容器、抗静电涂料、防腐涂层、电致发光材料、传感器、导电油墨等领域。
专利号为200680033112.0的中国发明专利公开了一种电解质电容器的制备方法，该方法至少包括以下步骤：a)使电极材料的多孔电极体(2)经阳极氧化反应以形成覆盖该电极材料表面的电介质(3)；b)在多孔主体上施加分散体A)，多孔主体至少包括电极材料的多孔电极体(2)和电介质(3)，分散体A)至少包含导电聚合物的颗粒B)和分散剂D)；c)为形成完全或部分覆盖电介质表面的固体电解质(4)，至少部分地去除和/或固化分散剂D)，多孔电极体(2)在阳极氧化期间的最大阳极化电压大于30V，分散体A)中导电聚合物颗粒B)的平均粒径为1-100nm。即：施加导电颗粒平均粒径为1-100nm，阳极氧化电压大于30V。经测试发现，上述发明的电解质电容器仍然存在出容性能与损耗、等效串联电阻、漏电性能无法兼顾的问题。
发明内容
本发明所要解决的技术问题是：提供一种可以控制合适的分子量，以使出容容易、损耗低、等效串联电阻低以及漏电低的铝电解质电容器，进一步提供上述铝电解质电容器的制备方法。
为了解决上述技术问题，本发明采用的技术方案为：
一种铝电解质电容器，所述铝电解质电容器的阳极的氧化电压大于30V，包括分散体，所述分散体包括导电聚合物和分散剂，所述导电聚合物的平均粒径为10-30nm。
本发明还提供一种铝电解质电容器的制备方法，在上述的铝电解质电容器的电极上施加所述分散体，然后将所述分散剂部分或全部去除，或者将所述分散剂进行固化，所述去除或固化的次数为一次或两次以上。
本发明的有益效果在于：
(1)当阳极的氧化电压大于30V，孔径较大时，控制导电聚合物的平均粒径为10-30nm的设计，达到出容容易的技术效果；
(2)获得的铝电解质电容器具有损耗低、等效串联电阻低以及漏电低的优点。
具体实施方式
为详细说明本发明的技术内容、所实现目的及效果，以下结合实施方式予以说明。
本发明最关键的构思在于：在阳极氧化电压大于30V的条件下，通过控制导电聚合物的平均粒径为10-30nm，从而达到出容容易的技术效果。
本发明提供一种铝电解质电容器，所述铝电解质电容器的阳极的氧化电压大于30V，包括分散体，所述分散体包括导电聚合物和分散剂，所述导电聚合物的平均粒径为10-30nm。
本发明还提供一种铝电解质电容器的制备方法，在上述的铝电解质电容器的电极上施加所述分散体，然后将所述分散剂部分或全部去除，或者将所述分散剂进行固化，所述去除或固化的次数为一次或两次以上。
本发明的技术构思为：
已知电容器电压与出容性能的关系为：随着电压的升高，多孔阳极的孔径变大，电压越低，孔径越小，出容将越难。
当分子量越小，则粒径越小，但是，其稳定性、导电性能会变差，因而当粒径为1-10nm，会因为粒径太小，使分散体电导率低，制备出的电容器等效串联电阻会变大；当分子量大，则粒径大，其稳定性会好，导电性能较优，但是，分子量过大，粒径又会太大，不利于进入多孔阳极的孔中；因而当粒径为 30-100nm，会因为粒径太大，不利于分散体进入到电极的孔中，制备获得的电容器出容率低且损耗高。因此，现有技术中的电解质电容器存在出容率、损耗性能、与等效串联电阻、导电性能(如漏电性能)不能兼顾的问题。
而本申请人正是基于上述问题的发现，发现当阳极的氧化电压大于30V时，控制导电颗粒粒径在10-30nm之间，PEDOT/PSS分散液剪切，均质后的粒径与聚苯乙烯磺酸(pss)的分子量关系密切；综合考虑分散液的稳定性、导电性和粒径，并通过长期的实验得出：在阳极的氧化电压大于30V，控制导电聚合物的平均粒径为10-30nm，此时该电压下其孔径与粒径的配合可以达到出容率高的技术效果；同时，当电压大于30V时的孔径较大，分散体容易进到孔中，孔内进入的分散体越多，做出的电容器性能就越好，因此获得的铝电解质电容器具有损耗低、等效串联电阻低以及漏电低的优点。
从上述描述可知，本发明的有益效果在于：
(1)当阳极的氧化电压大于30V，孔径较大时，控制导电聚合物的平均粒径为10-30nm的设计，达到出容容易的技术效果；
(2)获得的铝电解质电容器具有损耗低、等效串联电阻低以及漏电低的优点。
进一步的，所述导电聚合物包括聚噻吩衍生物，所述聚噻吩衍生物包括具有下述通式I和/或通式II组成的重复单元，所述通式I的结构式为：
Figure PCTCN2016094922-appb-000001
所述通式II的结构式为：
Figure PCTCN2016094922-appb-000002
所述通式I的结构式和通式II的结构式中，A为任选取代的碳原子数为1-5的亚烷基；R为任选取代的碳原子数为5-12的直连或支链环烷基、任选取代的碳原子数为6-14的直链或支链芳基、任选取代的碳原子数为7-18的直链或支链芳烷基、任选取代的碳原子数为1-4的直链或支链羟烷基或羟基；X为0-8的整数。
在A结合有几个A基团的情况下，这些基团可以相同或不同。
本发明的所述聚噻吩衍生物可以为具有通式I组成的重复单元，也可以为具有通式II组成的重复单元，亦可以为具有通式I和通式II组成的重复单元。
由上述描述可知，聚噻吩衍生物可以是任选被取代的聚噻吩，优选为上述包括具有下述通式I和/或通式II组成的重复单元。上述结构的聚噻吩衍生物可以更好的与阳极孔径大小进行配合，进一步提高出容的容易程度。
进一步的，所述导电聚合物还包括聚吡咯衍生物和聚苯胺衍生物中的至少一种。
进一步的，所述分散体还包括聚合阴离子。优选的，所述聚合阴离子为聚合羧酸阴离子或聚合磺酸阴离子。更为优选的，所述聚合阴离子为聚苯乙烯磺酸阴离子，所述聚苯乙烯磺酸阴离子的分子量为2000-500000。
由上述描述可知，分散体中添加聚合阴离子，聚阴离子可以做复合离子，与聚噻吩复合然后分散到水中，聚阴离子同时也可以作为掺杂剂，控制聚苯乙烯磺酸阴离子的分子量为2000-500000，可以使聚噻吩更好的分散在水中。其中，更为优选的，聚苯乙烯磺酸阴离子的分子量为10000-200000。
进一步的，所述分散剂为有机溶剂和/或水。
进一步的，所述分散体还包括交联剂、表面活性剂和添加剂中的至少一种，所述添加剂选自醚、内酯、酰胺基团、内酰胺基团、砜、亚砜、糖、糖衍生物、糖醇、呋喃衍生物、二元醇和多元醇中的至少一种。
由上述描述可知，所述交联剂和表面活性剂可以采用现有技术中的常用交联剂和表面活性剂。加入交联剂、表面活性剂和添加剂分别具有有效交联、降低表面张力的作用。
进一步的，所述分散体的pH值为1.5-7，所述分散体在20℃条件下的粘度不大于500cps。
由上述描述可知，可以对分散体的pH值和粘度进行上述控制，更为优选的，分散体的pH值为2-5，同时可以在60rpm的转速下对其粘度进行测试。
在本发明的铝电解质电容器的制备方法中：
分散体中的pH值可加入酸或碱来调节；所述“施加所述分散体，然后将所述分散剂部分或全部去除，或者将所述分散剂进行固化”的步骤可进行一次或重复两次以上。
另外，本发明的分散液的合成的设计、以及分散体原料的组成的筛选，可充分考虑分散液的稳定性、导电性和粒径，以获得良好的性质(出容容易、损耗低、等效串联电阻低以及漏电低)。
实施例1
本实施例的一种铝电解质电容器，所述铝电解质电容器的阳极的氧化电压为30V，包括分散体，所述分散体包括导电聚合物、分散剂和聚合阴离子，还包括添加剂，所述添加剂为醚、内酯、酰胺基团、呋喃衍生物和多元醇的混合物。所述分散体的pH值为1.5，所述分散体在20℃条件下的粘度为500cps。所述导电聚合物的平均粒径为10nm。所述导电聚合物包括聚噻吩衍生物，还包括聚吡咯衍生物。所述聚合阴离子为聚苯乙烯磺酸阴离子，所述聚苯乙烯磺酸阴离子的分子量为2000，所述分散剂为水。所述聚噻吩衍生物包括具有下述通式I组成的重复单元，所述通式I的结构式为：
Figure PCTCN2016094922-appb-000003
所述通式I的结构式中，A为任选取代的碳原子数为1的亚烷基；R为任选取代的碳原子数为5的直连或支链环烷基、任选取代的碳原子数为6的直链芳基、任选取代的碳原子数为7的直链芳烷基、任选取代的碳原子数为1的直链羟烷基或羟基；X为0。
实施例2
本实施例的一种铝电解质电容器，所述铝电解质电容器的阳极的氧化电压为50V，包括分散体，所述分散体包括导电聚合物、分散剂和聚合阴离子，还包括添加剂，所述添加剂为醚。所述分散体的pH值为7，所述分散体在20℃条件下的粘度为400cps。所述导电聚合物的平均粒径为30nm。所述导电聚合物包括聚噻吩衍生物，还包括聚吡咯衍生物和聚苯胺衍生物。所述聚合阴离子为聚苯乙烯磺酸阴离子，所述聚苯乙烯磺酸阴离子的分子量为500000，所述分散剂为有机溶剂。所述聚噻吩衍生物包括具有下述通式II组成的重复单元，所述通式II的结构式为：
Figure PCTCN2016094922-appb-000004
所述通式II的结构式中，A为任选取代的碳原子数为5的亚烷基；R为任选取代的碳原子数为12的支链环烷基、任选取代的碳原子数为14的支链芳基、任选取代的碳原子数为18的支链芳烷基、任选取代的碳原子数为4的支链羟烷基或羟基；X为8。
实施例3
本实施例的一种铝电解质电容器，所述铝电解质电容器的阳极的氧化电压为60V，包括分散体，所述分散体包括导电聚合物、分散剂和聚合阴离子，还包括添加剂，所述添加剂为酰胺基团。所述分散体的pH值为4，所述分散体在20℃条件下的粘度为200cps。所述导电聚合物的平均粒径为20nm。所述导电聚合物包括聚噻吩衍生物，还包括聚苯胺衍生物。所述聚合阴离子为聚苯乙烯磺酸阴离子，所述聚苯乙烯磺酸阴离子的分子量为300000，所述分散剂为水。所述聚噻吩衍生物包括具有下述通式I和通式II组成的重复单元，所述通式I的结构式为：
Figure PCTCN2016094922-appb-000005
所述通式II的结构式为：
Figure PCTCN2016094922-appb-000006
所述通式I的结构式和通式II的结构式中，A为任选取代的碳原子数为2的亚烷基；R为任选取代的碳原子数为8的直链环烷基、任选取代的碳原子数为10的直链芳基、任选取代的碳原子数为10的直链芳烷基、任选取代的碳原子数 为3的支链羟烷基或羟基；X为4。
实施例4
将100g聚苯乙烯磺酸(分子量25000)加入到2000g去离子水中，搅拌30分钟，然后将50g 35％的过硫酸钠水溶液，1％的硫酸铁水溶液14.4g与9.1g 3，4-二烷氧基噻吩混合均匀加入到上述水溶液中，搅拌24h。反应结束后，向反应体系中加入200g阳离子树脂，200g阴离子树脂搅拌2h，过滤掉树脂，即得到聚(3，4-二烷氧基噻吩)聚阴离子分散体。用高压均质机，在1000bar压力下，均质5次。然后测试固含量1.34％。用粒度测试仪测试粒径在10-30nm。分散体的粘度150cps。
将100g上述方法获得的聚(3，4-二烷氧基噻吩)聚阴离子、5g乙二醇、5g聚乙二醇600、0.5g3-缩水甘油氧基三甲氧基甲硅烷(Silquest A-187)、0.5gDynol604(Air product)在玻璃烧杯中用磁力搅拌器混匀，形成分散体B。
分别将4种规格的芯包含上述分散体B，然后于120℃下进行烘干并对其性能进行测试。测试结果如表1。表1为4种规格的芯包含分散体B的性能测试表。
表1 包含分散体B的四种规格芯的测试结果
Figure PCTCN2016094922-appb-000007
实施例5
将100g实施例1的聚(3，4-二烷氧基噻吩)聚阴离子分散体、5g二甲基亚砜、5g聚乙二醇400、0.5g 3-缩水甘油氧基三甲氧基甲硅烷(SilquestA-187)、2g山梨醇、0.5g Dynol604(Air product)在玻璃烧杯中用磁力搅拌器混匀，形成分散体C。
分别将4种规格的芯包含所述分散体C，然后于120℃下进行烘干并对其性能进行测试。测试结果如表2。表2为4种规格的芯包含分散体C的性能测试表。
表2 包含分散体C的四种规格芯的测试结果
Figure PCTCN2016094922-appb-000008
实施例6
将100g实施例1的聚(3，4-二烷氧基噻吩)聚阴离子分散体、5g二甲基亚砜、5g聚乙二醇200、0.5g 3-缩水甘油氧基三甲氧基甲硅烷(SilquestA-187)、2g木糖醇、0.5g Dynol604(Air product)在玻璃烧杯中用磁力搅拌器混匀，形成分散体D。
分别将4种规格的芯包含分散体D，然后于120℃下进行烘干并对其性能进行测试。
测试结果如表3。表3为4种规格的芯包含分散体D的性能测试表。
表3 包含分散体D的四种规格芯的测试结果
Figure PCTCN2016094922-appb-000009
由表1-3可知，本申请的铝电解质电容器的电容为10-220μF，DF值为1.4-1.6％，等效串联电阻为6-18mΩ，具有出容容易、损耗低、等效串联电阻低以及漏电低的优点。
综上所述，本申请提供的铝电解质电容器具有出容容易、损耗低、等效串联电阻低以及漏电低的优点。
以上内容是结合具体的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干简单推演或替换， 都应当视为属于本申请的保护范围。

Claims (10)

  1. 一种铝电解质电容器，其特征在于，所述铝电解质电容器的阳极的氧化电压大于30V，包括分散体，所述分散体包括导电聚合物和分散剂，所述导电聚合物的平均粒径为10-30nm。
  2. 根据权利要求1所述的铝电解质电容器，其特征在于，所述导电聚合物包括聚噻吩衍生物，所述聚噻吩衍生物包括具有下述通式I和/或通式II组成的重复单元，所述通式I的结构式为：
    Figure PCTCN2016094922-appb-100001
    所述通式II的结构式为：
    Figure PCTCN2016094922-appb-100002
    所述通式I的结构式和通式II的结构式中，A为任选取代的碳原子数为1-5的亚烷基；R为任选取代的碳原子数为5-12的直连或支链环烷基、任选取代的碳原子数为6-14的直链或支链芳基、任选取代的碳原子数为7-18的直链或支链芳烷基、任选取代的碳原子数为1-4的直链或支链羟烷基或羟基；X为0-8的整数。
  3. 根据权利要求1所述的铝电解质电容器，其特征在于，所述导电聚合物还包括聚吡咯衍生物和聚苯胺衍生物中的至少一种。
  4. 根据权利要求1所述的铝电解质电容器，其特征在于，所述分散体还包括聚合阴离子。
  5. 根据权利要求4所述的铝电解质电容器，其特征在于，所述聚合阴离子为聚合羧酸阴离子或聚合磺酸阴离子。
  6. 根据权利要求4所述的铝电解质电容器，其特征在于，所述聚合阴离子为聚苯乙烯磺酸阴离子，所述聚苯乙烯磺酸阴离子的分子量为2000-500000。
  7. 根据权利要求1所述的铝电解质电容器，其特征在于，所述分散剂为有机 溶剂和/或水。
  8. 根据权利要求1所述的铝电解质电容器，其特征在于，所述分散体还包括交联剂、表面活性剂和添加剂中的至少一种，所述添加剂选自醚、内酯、酰胺基团、内酰胺基团、砜、亚砜、糖、糖衍生物、糖醇、呋喃衍生物、二元醇和多元醇中的至少一种。
  9. 根据权利要求1所述的铝电解质电容器，其特征在于，所述分散体的pH值为1.5-7，所述分散体在20℃条件下的粘度不大于500cps。
  10. 一种铝电解质电容器的制备方法，其特征在于，在权利要求1-9任意一项所述的铝电解质电容器的电极上施加所述分散体，然后将所述分散剂部分或全部去除，或者将所述分散剂进行固化，所述去除或固化的次数为一次或两次以上。
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CN101263568A (zh) * 2005-09-13 2008-09-10 H.C.施塔克有限公司 电解质电容器的制备方法
CN103154132A (zh) * 2010-10-01 2013-06-12 赫劳斯贵金属有限两和公司 具有改进的电性能参数且包含pedot/pss和稳定剂的层组合物
CN103201804A (zh) * 2010-10-01 2013-07-10 赫劳斯贵金属有限两和公司 一种借助聚亚烷基二醇提高包含pedot/pss作为固体电解质的电容器的电性能参数的方法
CN105273168A (zh) * 2015-10-29 2016-01-27 深圳新宙邦科技股份有限公司 一种聚合物分散体的制备方法及制得的聚合物分散体及其用途
CN105761937A (zh) * 2016-02-25 2016-07-13 深圳新宙邦科技股份有限公司 一种铝电解质电容器及其制备方法

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