WO2017143736A1 - Condensateur électrolytique en aluminium et son procédé de fabrication - Google Patents

Condensateur électrolytique en aluminium et son procédé de fabrication Download PDF

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Publication number
WO2017143736A1
WO2017143736A1 PCT/CN2016/094921 CN2016094921W WO2017143736A1 WO 2017143736 A1 WO2017143736 A1 WO 2017143736A1 CN 2016094921 W CN2016094921 W CN 2016094921W WO 2017143736 A1 WO2017143736 A1 WO 2017143736A1
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WO
WIPO (PCT)
Prior art keywords
electrolytic capacitor
aluminum electrolytic
dispersion
formula
capacitor according
Prior art date
Application number
PCT/CN2016/094921
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English (en)
Chinese (zh)
Inventor
赵大成
李付亚
Original Assignee
深圳新宙邦科技股份有限公司
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Application filed by 深圳新宙邦科技股份有限公司 filed Critical 深圳新宙邦科技股份有限公司
Publication of WO2017143736A1 publication Critical patent/WO2017143736A1/fr

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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 a porous electrode body of an electrode material to anodization to form a dielectric covering a surface of the electrode material; b) Applying a dispersion on the porous body, the porous body comprising at least a porous electrode body of an electrode material and a dielectric, the dispersion comprising at least particles and a dispersant of the conductive polymer; c) forming a solid electrolyte completely or partially covering the surface of the dielectric, The dispersant is at least partially removed and/or cured, the maximum anodization voltage of the porous electrode body during anodization is greater than 30 V, and the average particle diameter of the conductive polymer particles in the dispersion is from 1 to 100 nm.
  • the pore size of the porous anode becomes larger, and the lower the voltage, the smaller the pore diameter, and the smaller the pore size, the more difficult the extraction is.
  • the electrolytic capacitor of the above patent is used for a voltage lower than 30 V, the pore diameter of the porous anode is greatly reduced, so that normal discharge cannot be ensured.
  • the technical problem to be solved by the present invention is to provide an aluminum electrolytic capacitor capable of ensuring that the aperture is at a certain size under a low voltage condition to facilitate discharge, 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 not more than 30 V, comprising a dispersion comprising a conductive polymer and a dispersant, the conductive polymer having an average particle diameter of 5 to 40 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 5-40 nm under the condition that the anodization voltage is not more than 30 V, the technical effect of easy discharge is achieved.
  • the present invention provides an aluminum electrolytic capacitor having an oxidation voltage of not more than 30 V, including a dispersion, the dispersion comprising a conductive polymer and a dispersant, the conductive polymer having an average particle diameter of 5 -40 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 conductive polymer includes a polythiophene derivative
  • the polythiophene derivative includes There are repeating units of the formula I and/or formula II, which have the structural formula:
  • 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 1000 to 1,000,000.
  • a polymeric anion is added to the dispersion, and the polyanion can be used as a composite ion, which is compounded with polythiophene and then dispersed into water.
  • the polyanion can also act as a dopant to control the molecular weight of the polystyrene sulfonate anion to be 1000- 1000000, the polythiophene can be better dispersed in water.
  • the polystyrenesulfonate anion has a molecular weight of 20,000 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.
  • An aluminum electrolytic capacitor of the embodiment wherein an anode of the aluminum electrolytic capacitor has an oxidation voltage of 25 V, comprising a dispersion comprising a conductive polymer, a dispersant, and a polymeric anion, 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 5 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 1000, 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 15 V, and includes a dispersion comprising a conductive polymer, a dispersant, and a polymerization 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 40 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 1,000,000, 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 5 V, and includes a dispersion comprising a conductive polymer, a dispersant, and a polymeric anion, and 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 having a molecular weight of 800,000 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.
  • R is an optionally substituted linear cycloalkyl group having 8 carbon atoms.
  • 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 219-380 ⁇ F, a DF value of 1.4-1.8%, and an equivalent series resistance of 5-9 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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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un condensateur électrolytique en aluminium et son procédé de fabrication. Un potentiel d'oxydation d'une anode du condensateur électrolytique en aluminium ne dépasse pas 30V et comprend une dispersion comprenant un polymère électroconducteur et un dispersant. Ledit polymère électroconducteur présente une taille particulaire moyenne de 5 à 40 nm. Le condensateur électrolytique en aluminium présente les avantages d'une fabrication facile, d'une faible perte, d'une faible résistance équivalente série et d'un faible courant de fuite.
PCT/CN2016/094921 2016-02-25 2016-08-12 Condensateur électrolytique en aluminium et son procédé de fabrication WO2017143736A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610102588.0A CN105761938B (zh) 2016-02-25 2016-02-25 一种铝电解质电容器及其制备方法
CN201610102588.0 2016-02-25

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WO2017143736A1 true WO2017143736A1 (fr) 2017-08-31

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105761938B (zh) * 2016-02-25 2019-02-15 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
JP7100029B2 (ja) * 2017-05-31 2022-07-12 綜研化学株式会社 導電性高分子固体電解コンデンサの製造方法及び導電性高分子

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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
CN104952621A (zh) * 2015-05-04 2015-09-30 深圳新宙邦科技股份有限公司 铝电解电容器用电解液及使用该电解液的铝电解电容器
CN105761938A (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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DE102005043829A1 (de) * 2005-09-13 2007-04-05 H.C. Starck Gmbh Verfahren zur Herstellung von Elektrolytkondensatoren mit hoher Nennspannung
US8279585B2 (en) * 2008-12-09 2012-10-02 Avx Corporation Cathode for use in a wet capacitor
US8824121B2 (en) * 2010-09-16 2014-09-02 Avx Corporation Conductive polymer coating for wet electrolytic capacitor
US8824122B2 (en) * 2010-11-01 2014-09-02 Avx Corporation Solid electrolytic capacitor for use in high voltage and high temperature applications
US8687347B2 (en) * 2011-01-12 2014-04-01 Avx Corporation Planar anode for use in a wet electrolytic capacitor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104952621A (zh) * 2015-05-04 2015-09-30 深圳新宙邦科技股份有限公司 铝电解电容器用电解液及使用该电解液的铝电解电容器
CN105761938A (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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CN105761938B (zh) 2019-02-15

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