WO2022218130A1 - 一种铝电解电容器用分散体及铝电解电容器 - Google Patents

一种铝电解电容器用分散体及铝电解电容器 Download PDF

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WO2022218130A1
WO2022218130A1 PCT/CN2022/083006 CN2022083006W WO2022218130A1 WO 2022218130 A1 WO2022218130 A1 WO 2022218130A1 CN 2022083006 W CN2022083006 W CN 2022083006W WO 2022218130 A1 WO2022218130 A1 WO 2022218130A1
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Prior art keywords
electrolytic capacitor
aluminum electrolytic
dispersion
compound
additive
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PCT/CN2022/083006
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English (en)
French (fr)
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曹宗泽
康媛媛
王涵
赵大成
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深圳新宙邦科技股份有限公司
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Priority to JP2023552144A priority Critical patent/JP2024509119A/ja
Priority to KR1020237029069A priority patent/KR20230147635A/ko
Publication of WO2022218130A1 publication Critical patent/WO2022218130A1/zh

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    • 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
    • H01G9/004—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 invention relates to the technical field of solid electrolytic capacitors, in particular to a dispersion for an aluminum electrolytic capacitor and an aluminum electrolytic capacitor.
  • Solid electrolytic capacitors use solid conductive materials with high conductivity and good thermal stability as electrolytes. Compared with ordinary electrolytic capacitors, they not only have all the characteristics of ordinary electrolytic capacitors, but especially have good reliability, long service life, high frequency It can be used in computer, communication, military, industrial control and other fields, as well as in a new generation of high-end complete machine products of consumer electronic products such as cameras, video recorders, flat-panel TVs, game consoles, etc., which is conducive to the integration of electronic products. and miniaturization, and can overcome the shortcomings of liquid electrolytic capacitors that are easy to leak and have a short life. With the rapid development of the domestic electronic information industry, polymer solid electrolytic capacitors will gradually replace ordinary low-voltage electrolytic capacitors from the development trend in recent years, and will become one of the pillar products of the electronic information industry in the 21st century.
  • Adding appropriate additives to the dispersion is an effective way to improve the conductivity of polymers.
  • Polyethylene glycol and its derivatives, polyglycerol are used in the prior art, and the main function is to increase the breakdown voltage.
  • the Chinese invention patent publication No. CN103429796A discloses reducing the ESR of a capacitor comprising PEDOT/PSS as a solid electrolyte by means of polyglycerol, but the increase in capacity is not obvious.
  • the purpose of the present invention is to overcome the problems of low capacity extraction and large ESR of solid electrolytic capacitors in the prior art.
  • the present invention provides a dispersion for an aluminum electrolytic capacitor and an aluminum electrolytic capacitor prepared by using the dispersion.
  • a dispersion for aluminum electrolytic capacitors comprising a dispersant, a conductive polymer and an additive dispersed in the dispersant, wherein the additive is selected from one or more of the compounds represented by the following structural formula,
  • the compound has at least one hydroxyl group and at least one ether group, wherein R1 and R2 are independently selected from sulfur-containing groups, carbon-containing groups and hydrogen, and n is an integer of 1-10.
  • n is 1-10, the water-solubility of the dispersant is better. If n>10, the water-solubility of the dispersant will be deteriorated and the overall performance of the capacitor will be affected.
  • n is an integer of 1-5.
  • R1 and R2 are independently selected from sulfonate, sulfate, carbonyl, hydroxyacetone, glycerol, propylene glycol, hydrogen, and alkyl.
  • R1 and R2 are selected from hydroxyacetone, glycerol and propylene glycol.
  • R1 or R2 carries hydroxyl groups or both ends carry hydroxyl groups.
  • the compound shown in the structural formula has both ether bonds and hydroxyl groups, which can greatly improve the bonding tightness between the conductive polymer and the dielectric oxide layer, which is important for improving the capacity of capacitors, It is extremely advantageous to reduce the ESR value.
  • the additive is selected from one or more of the following compounds 1-12:
  • the content of the additive is 0.01%-10%, and more preferably the content of the additive is 0.1%-5%.
  • the content of the additive is too high, the viscosity of the dispersion will rise, affecting the impregnation effect, and adversely affecting the performance of the capacitor; while when the content of the additive is too low, it cannot significantly improve the performance.
  • the conductive polymer is selected from one or more of polythiophene, polypyrrole, polyaniline, and derivatives thereof.
  • Polythiophene and its derivatives are preferred, and poly(3,4-ethylenedioxythiophene) is more preferred.
  • dispersing agent is selected from organic solvents and/or water, and the dispersing agent is preferably water. Dispersions can be prepared by methods known in the art.
  • the present invention also provides an aluminum electrolytic capacitor, comprising: an anode body with a dielectric layer on the surface, a cathode body, a separator, and a solid electrolyte layer covering at least a part of the dielectric layer, the solid electrolyte layer is made of the above dispersion prepared.
  • compounds with a polyhydroxy ether structure are used as additives to improve the capacity extraction of aluminum electrolytic capacitors and reduce the ESR value, mainly because the polyhydroxy structure can promote the conductive polymer.
  • the cross-linking effect can also improve the bonding tightness of the electrolyte layer generated by the conductive polymer and the Al 2 O 3 film of the dielectric layer, thereby improving the capacity extraction rate of the aluminum electrolytic capacitor, and reducing the loss value and equivalent resistance of the aluminum electrolytic capacitor.
  • the compound represented by the structural formula of 1 ⁇ n ⁇ 10 can be better dissolved in the dispersion, and the dispersion system will not be damaged, so that the dispersion will not increase in viscosity or coagulate. glue.
  • the core package used in the preparation of the electrolytic capacitor in the present invention selects a winding core package with a size of 16V1000 and a size of 10*13.
  • This example is used to illustrate the preparation method of the aluminum electrolytic capacitor dispersion disclosed in the present invention, and the aluminum electrolytic capacitor prepared by using the dispersion.
  • the mass fraction of compound 1 is 5% of the total amount of the mixture, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the present invention Aluminum Electrolytic Capacitor Dispersion.
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that the mass fraction of compound 1 is 0.1% of the total amount of the mixture, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 1 is 0.1% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that the mass fraction of compound 1 is 3% of the total amount of the mixed solution, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 1 is 3% of the total amount of the mixture, stir with a magnetic stirrer at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that the mass fraction of compound 1 is 0.01% of the total amount of the mixture, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 1 is 0.01% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that the mass fraction of compound 1 is 10% of the total amount of the mixture, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 1 is 10% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the difference of this example is only that Compound 1 is not added, and other parameters and methods are the same as Example 1. details as follows:
  • the PEDOT/PSS is stirred at room temperature with a magnetic stirrer for 6 hours, and then homogenized by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention.
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with glycerol, and other parameters and methods are the same as those in Example 1. details as follows:
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with polyethylene glycol 400, and other parameters and methods are the same as those in Example 1. details as follows:
  • polyethylene glycol 400 to PEDOT/PSS. As shown in Table 1, the mass fraction of polyethylene glycol 400 is 5% of the total amount of the mixture. Use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer. quality, that is, the aluminum electrolytic capacitor dispersion of the present invention is obtained.
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 2, and the mass fraction of compound 2 is 3% of the total amount of the mixture.
  • Other parameters and methods are the same as the examples in the examples. 1 is the same. details as follows:
  • the mass fraction of compound 2 is 3% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention. .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 3, and the mass fraction of compound 3 is 2% of the total amount of the mixture. Other parameters and methods are the same as the examples in the examples. 1 is the same. details as follows:
  • the mass fraction of compound 3 is 2% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 5, and the mass fraction of compound 5 is 1% of the total amount of the mixture. Other parameters and methods are the same as those in the examples. 1 is the same. details as follows:
  • the mass fraction of compound 5 is 1% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 8, and the mass fraction of compound 8 is 1% of the total amount of the mixture.
  • Other parameters and methods are the same as the examples in the examples. 1 is the same. details as follows:
  • the mass fraction of compound 8 is 1% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 4, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 4 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 6, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 6 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 7, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 7 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 9, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 9 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention. .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced with compound 10, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 10 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that compound 1 is replaced by compound 11, and other parameters and methods are the same as those in Example 1. details as follows:
  • the mass fraction of compound 11 is 5% of the total amount of the mixture, stir with a magnetic stirrer at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example 1 As shown in Table 1, compared with Example 1, the only difference in this example is that Compound 1 is replaced with Compound 12, and other parameters and methods are the same as those of Example 1. details as follows:
  • the mass fraction of compound 12 is 5% of the total amount of the mixed solution, use a magnetic stirrer to stir at room temperature for 6 hours, and then homogenize by a homogenizer to obtain the aluminum electrolytic capacitor dispersion of the present invention .
  • the electrolytic capacitor core pack was immersed in the aluminum electrolytic capacitor dispersion prepared in this example for 30 min under negative pressure and dried, and the above steps were repeated 3 times, and then the aluminum electrolytic capacitor was assembled by sealing.
  • Example/Comparative Example additive Quality Score Example 1 Compound 1 5%
  • Example 2 Compound 1 0.1%
  • Example 3 Compound 1 3%
  • Example 4 Compound 1 0.01%
  • Example 5 Compound 1 10% Comparative Example 1 - - Comparative Example 2 glycerin 5% Comparative Example 3 polyethylene glycol 400 5%
  • Example 6 Compound 2 3%
  • Example 7 Compound 3 2%
  • Example 8 Compound 5 1%
  • Example 9 Compound 8 1%
  • Example 10 Compound 4 5%
  • Example 11 Compound 6 5%
  • Example 12 Compound 7 5%
  • Example 13 Compound 9 5%
  • Example 14 Compound 10 5%
  • Example 15 Compound 11 5%
  • Example 16 Compound 12 5%
  • test results of above embodiment and comparative example are as shown in table 2 below:
  • Example 13 1056 2.21 6.18
  • Example 14 1049 2.31 6.45
  • Example 15 1039 2.45 6.67
  • Example 16 1042 2.49 6.31
  • the electrolytic capacitor prepared by the dispersion for aluminum electrolytic capacitor of the present invention has an electrostatic capacity (Cap) ⁇ 1021 ⁇ F, a capacitance loss value (DF) ⁇ 3.01%, and an equivalent resistance (ESR) ⁇ 7.02m ⁇ , the electrolytic capacitor of the present invention has higher electrostatic capacity, lower capacitance loss value and equivalent resistance.
  • the additive of the present invention can improve the capacity extraction rate of the aluminum electrolytic capacitor, and reduce the loss value and the equivalent resistance of the aluminum electrolytic capacitor, and the large Significantly improve the conductivity and stability of aluminum electrolytic capacitors.

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Abstract

本发明涉及固态电解电容技术领域，特别涉及一种铝电解电容器用分散体及铝电解电容器。所述分散体包括分散剂，以及分散于所述分散剂中的导电聚合物和添加剂，所述添加剂选自如下结构式所示化合物中的一种或多种，所述化合物具有至少一个羟基和至少一个醚基，其中，R1、R2相互独立的选自含硫基团、含碳基团、氢，n为1-10的整数。本发明的分散体使用具有多羟基醚结构的添加剂提升铝电解电容器的容量引出以及降低等效电阻，多羟基结构的添加剂可以促进导电高分子之间的交联作用，同时可以提升导电聚合物生成的电解质层与介质层Al 2O3膜的结合紧密性，从而提升铝电解电容器的容量引出率，并且降低铝电解电容器的损耗值以及等效电阻。

Description

一种铝电解电容器用分散体及铝电解电容器 技术领域
本发明涉及固态电解电容技术领域，特别涉及一种铝电解电容器用分散体及铝电解电容器。
背景技术
固体电解电容器采用导电率高、热稳定度佳的固体导电材料作为电解质，与普通电解电容器相比，它不但具有普通电解电容器所有特性，尤其具有可靠性好、使用寿命长、高频低阻抗、耐特大纹波电流等特性，可用于计算机、通信、军事、工业控制等领域及照相机、录像机、平板电视、游戏机等消费类电子产品的新一代高档整机产品中，有利于电子产品的集成化和小型化，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，高分子固体电解电容器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解质电导率，降低电容器的等效电阻(ESR值)成为研究者共同追求的目标。但是，目前常用的添加剂与导电高分子聚合物存在相容性差、分散性不好等问题，阻碍了电荷的传输以及电导率的提高。尤为重要的是，在充放电过程中，固态电解电容器容量引出率会迅速下降，ESR值迅速增大，从而导致固态电解电容器性能迅速劣化而失效。
在分散体中加入适当的添加剂是提高聚合物导电性的一种有效途径。现有技术中使用聚乙二醇及其衍生物、聚甘油，主要作用是提升击穿电压。例如，公开号为CN103429796A的中国发明专利公开的借助聚甘油降低包含 PEDOT/PSS作为固体电解质的电容器的ESR，但对于容量的提升并不明显。
发明内容
本发明目的是为克服现有技术中固态电解电容器容量引出较低，ESR较大的问题。为解决上述问题，本发明提供一种铝电解电容器用分散体以及采用该分散体制备得到的铝电解电容器。
本发明解决上述技术问题所采用的技术方案如下：
提供一种铝电解电容器用分散体，包括分散剂，以及分散于所述分散剂中的导电聚合物和添加剂，所述添加剂选自如下结构式所示化合物中的一种或多种，
Figure PCTCN2022083006-appb-000001
所述化合物具有至少一个羟基和至少一个醚基，其中，R1、R2相互独立的选自含硫基团、含碳基团、氢，n为1-10的整数。n为1-10时分散剂的水溶性较好，若n＞10，会导致此分散剂的水溶性变差，影响电容器的整体性能。优选的，n为1-5的整数。
进一步的，R1、R2相互独立的选自磺酸根、硫酸根、羰基、羟基丙酮基、丙三醇基、丙二醇基、氢、烷基。
进一步的，R1、R2至少有一个选自羟基丙酮基、丙三醇基、丙二醇基。R1或R2携带羟基或者两端都携带羟基，结构式所示的化合物中既有醚键，又有羟基，能够极大提高导电聚合物与介质氧化层的结合紧密性，这对于提升电容器的容量、降低ESR值是极为有利的。
进一步的，所述添加剂选自如下化合物1～12中的一种或多种：
Figure PCTCN2022083006-appb-000002
进一步的，相对于所述分散体的总质量，所述添加剂的含量为0.01％-10％，进一步优选的所述添加剂的含量为0.1％-5％。当添加剂的含量过高时，会导致分散体粘度上升，影响含浸效果，对电容器的性能造成不利影响；而当添加剂的含量过低时，则无法起到明显的改善性能的作用。
进一步的，所述导电聚合物选自聚噻吩、聚吡咯、聚苯胺、及其衍生物中的一种或多种。优选聚噻吩及其衍生物，进一步优选聚(3,4-亚乙基二氧噻吩)。
进一步的，所述分散剂选自有机溶剂和/或水，所述分散剂优选水。分散体可以通过现有已知的方法制备获得。
本发明还提供一种铝电解电容器，其包括：表面具有介电层的阳极体、阴极体、隔膜以及覆盖介电层至少一部分的固体电解质层，所述固体电解质层是 由以上所述分散体制备而成。
本发明提供的一种铝电解电容器用分散体及铝电解电容器，具有如下有益效果：
(1)本发明的铝电解电容器用分散体，使用具有多羟基醚结构的化合物作为添加剂提升铝电解电容器的容量引出以及降低ESR值，其主要是由于多羟基结构可以促进导电高分子之间的交联作用，同时可以提升导电聚合物生成的电解质层与介质层Al 2O 3膜的结合紧密性，从而提升铝电解电容器的容量引出率，并且降低铝电解电容器的损耗值以及等效电阻。
(2)本发明的铝电解电容器用分散体，1≤n≤10的结构式所示化合物能够更好的溶解在分散体中，不会破坏分散体系，使得分散体不会出现粘度增大或凝胶。
具体实施方式
下面将结合具体实施例，对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。
本发明制备电解电容器采用的芯包选用16V1000规格，10*13尺寸大小的卷绕芯包。
实施例1
本实施例用于说明本发明公开的铝电解电容器分散体的制备方法，以及采用该分散体制备的铝电解电容器。
向PEDOT/PSS中加入化合物1，如表1所示，化合物1的质量分数为混合 液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例2
如表1所示，与实施例1相比，本实施例的区别仅在于，化合物1的质量分数为混合液总量的0.1％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物1，化合物1的质量分数为混合液总量的0.1％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例3
如表1所示，与实施例1相比，本实施例的区别仅在于，化合物1的质量分数为混合液总量的3％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物1，化合物1的质量分数为混合液总量的3％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例4
如表1所示，与实施例1相比，本实施例的区别仅在于，化合物1的质量分数为混合液总量的0.01％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物1，化合物1的质量分数为混合液总量的0.01％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例5
如表1所示，与实施例1相比，本实施例的区别仅在于，化合物1的质量分数为混合液总量的10％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物1，化合物1的质量分数为混合液总量的10％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
对比例1
如表1所示，与实施例1相比，本实施例的区别仅在于未添加化合物1，其它参数及方法与实施例1相同。具体如下：
将PEDOT/PSS使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
对比例2
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为甘油，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入甘油，如表1所示，甘油的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
对比例3
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为聚乙二醇400，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入聚乙二醇400，如表1所示，聚乙二醇400的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例6
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物2，化合物2的质量分数为混合液总量的3％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物2，化合物2的质量分数为混合液总量的3％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例7
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物3，化合物3的质量分数为混合液总量的2％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物3，化合物3的质量分数为混合液总量的2％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例8
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物5，化合物5的质量分数为混合液总量的1％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物5，化合物5的质量分数为混合液总量的1％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例9
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物8，化合物8的质量分数为混合液总量的1％，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物8，化合物8的质量分数为混合液总量的1％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电 容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例10
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物4，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物4，化合物4的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例11
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物6，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物6，化合物6的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例12
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物7，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物7，化合物7的质量分数为混合液总量的5％， 使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例13
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物9，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物9，化合物9的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例14
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物10，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物10，化合物10的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例15
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物11，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物11，化合物11的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
实施例16
如表1所示，与实施例1相比，本实施例的区别仅在于，将化合物1替换为化合物12，其它参数及方法与实施例1相同。具体如下：
向PEDOT/PSS中加入化合物12，化合物12的质量分数为混合液总量的5％，使用磁力搅拌器常温搅拌6h，再通过均质机进行均质，即得本发明的铝电解电容器分散体。
将电解电容器芯包负压条件下浸没于本例制备的铝电解电容器分散体中30min并干燥，重复上述步骤3次，再经过封口装配成铝电解电容器。
对实施例1-16及对比例1-3制备的电解电容器进行性能测试：使用自动电子零件分析仪对电容器在120Hz频率下的静电容量、损耗值和100kHz频率下的等效电阻进行测试。
表1 实施例1-16及对比例1-3的分散体中化合物种类及含量
实施例/对比例 添加剂 质量分数
实施例1 化合物1 5％
实施例2 化合物1 0.1％
实施例3 化合物1 3％
实施例4 化合物1 0.01％
实施例5 化合物1 10％
对比例1 - -
对比例2 甘油 5％
对比例3 聚乙二醇400 5％
实施例6 化合物2 3％
实施例7 化合物3 2％
实施例8 化合物5 1％
实施例9 化合物8 1％
实施例10 化合物4 5％
实施例11 化合物6 5％
实施例12 化合物7 5％
实施例13 化合物9 5％
实施例14 化合物10 5％
实施例15 化合物11 5％
实施例16 化合物12 5％
以上实施例和对比例的测试结果如下表2所示：
表2 实施例1-16及对比例1-3的制备的电解电容器的性能测试
实施例 Cap(μF) DF(％) ESR(mΩ)
实施例1 1051 2.18 6.11
实施例2 1040 2.53 6.78
实施例3 1048 2.21 6.24
实施例4 1021 2.98 6.97
实施例5 1039 3.01 7.02
对比例1 962 5.89 10.18
对比例2 1001 3.56 8.59
对比例3 1010 3.48. 8.34
实施例6 1046 2.37 6.56
实施例7 1053 2.23 6.45
实施例8 1039 2.45 6.78
实施例9 1035 2.47 6.91
实施例10 1049 2.23 6.37
实施例11 1050 2.31 6.47
实施例12 1052 2.19 6.32
实施例13 1056 2.21 6.18
实施例14 1049 2.31 6.45
实施例15 1039 2.45 6.67
实施例16 1042 2.49 6.31
由表2中数据可以看出，由本发明的铝电解电容器用分散体制备的电解电容器，静电容量(Cap)≥1021μF，电容损耗值(DF)≤3.01％，等效电阻(ESR)≤7.02mΩ，本发明的电解电容器具有较高的静电容量，较低的电容损耗值和等效电阻。
由表2中实施例1-5的测试结果可以看出，化合物1在分散体中的含量对电解电容器导电性能的提升密切相关。当化合物1的含量在0.1％-5％时，其分散体制备的电解电容器性能提升明显；当化合物1含量偏低时，分散体对氧化铝膜吸附作用较弱，对铝电解电容器无法起到明显的改善性能的作用；当化合物1含量偏高时，会导致分散体粘度上升，影响含浸效果，同时对电容器的性能造成影响。由表2中对比例1-3的测试结果可以看出，相对于现有技术，本发明的添加剂可提升铝电解电容器的容量引出率，并且降低铝电解电容器的损耗值以及等效电阻，大幅度提升铝电解电容器的导电性能及稳定性。
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 (8)

  1. 一种铝电解电容器用分散体，其特征在于，包括分散剂，以及分散于所述分散剂中的导电聚合物和添加剂，所述添加剂选自如下结构式所示化合物中的一种或多种，
    Figure PCTCN2022083006-appb-100001
    所述化合物具有至少一个羟基和至少一个醚基，其中，R1、R2相互独立的选自含硫基团、含碳基团、氢，n为1-10的整数。
  2. 根据权利要求1所述的分散体，其特征在于，R1、R2相互独立的选自磺酸根、硫酸根、羰基、羟基丙酮基、丙三醇基、丙二醇基、氢、烷基。
  3. 根据权利要求2所述的分散体，其特征在于，R1、R2至少有一个选自羟基丙酮基、丙三醇基、丙二醇基。
  4. 根据权利要求1所述的分散体，其特征在于，所述添加剂选自如下化合物1～12中的一种或多种：
    Figure PCTCN2022083006-appb-100002
    Figure PCTCN2022083006-appb-100003
  5. 根据权利要求1～4任意一项所述的分散体，其特征在于，相对于所述分散体的总质量，所述添加剂的含量为0.01％-10％。
  6. 根据权利要求1～4任意一项所述的分散体，其特征在于，所述导电聚合物选自聚噻吩、聚吡咯、聚苯胺、及其衍生物中的一种或多种。
  7. 根据权利要求1所述的分散体，其特征在于，所述分散剂选自有机溶剂和/或水。
  8. 一种铝电解电容器，其包括：表面具有介电层的阳极体、阴极体、隔膜以及覆盖介电层至少一部分的固体电解质层，其特征在于，所述固体电解质层是由权利要求1～7中任意一项所述分散体制备而成。
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CN104078239A (zh) * 2014-06-25 2014-10-01 福建国光电子科技股份有限公司 固体电解电容器制备固体电解质层的聚合溶液
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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* Cited by examiner, † Cited by third party
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CN104078239A (zh) * 2014-06-25 2014-10-01 福建国光电子科技股份有限公司 固体电解电容器制备固体电解质层的聚合溶液
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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