WO2021172199A1 - 電解コンデンサおよびその製造方法 - Google Patents

電解コンデンサおよびその製造方法 Download PDF

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Publication number
WO2021172199A1
WO2021172199A1 PCT/JP2021/006350 JP2021006350W WO2021172199A1 WO 2021172199 A1 WO2021172199 A1 WO 2021172199A1 JP 2021006350 W JP2021006350 W JP 2021006350W WO 2021172199 A1 WO2021172199 A1 WO 2021172199A1
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conductive polymer
compound
monomer unit
electrolytic capacitor
dielectric layer
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French (fr)
Japanese (ja)
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高谷　和宏
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202180015052.4A priority Critical patent/CN115104165A/zh
Priority to JP2022503331A priority patent/JP7702641B2/ja
Publication of WO2021172199A1 publication Critical patent/WO2021172199A1/ja
Priority to US17/815,261 priority patent/US12266482B2/en
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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
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • H01G9/0032—Processes of manufacture formation of the dielectric 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
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • 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
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure

Definitions

  • This disclosure relates to electrolytic capacitors and their manufacturing methods.
  • an electrolytic capacitor having an anode forming a dielectric layer and a conductive polymer covering at least a part of the dielectric layer is promising.
  • the conductive polymer poly (3,4-ethylenedioxythiophene) (PEDOT) polymerized with 3,4-ethylenedioxythiophene (EDOT) is often used (Patent Document 1, Patent Document 2, etc.). ..
  • Patent Document 3 includes a conductive polymer and a conductive auxiliary liquid, and the conductive auxiliary liquid is an aromatic compound having a high boiling point organic solvent having a boiling point of 150 ° C. or higher and at least one hydroxy group.
  • electrolytic capacitors including.
  • the electrolytic capacitor according to the first aspect of the present disclosure includes a capacitor element including an anode having a dielectric layer on its surface and a conductive polymer covering a part of the dielectric layer.
  • the conductive polymer contains a first monomer unit corresponding to the 3,4-ethylenedioxythiophene compound and a second monomer unit corresponding to the 3,4-dialkoxythiophene compound.
  • the method for manufacturing an electrolytic capacitor according to the second aspect of the present disclosure includes a first step of preparing an anode, a second step of forming a dielectric layer on the surface of the anode, and the dielectric layer being formed.
  • the present invention includes a third step of treating the anode with a treatment liquid containing a conductive polymer or a precursor thereof.
  • the conductive polymer contains a first monomer unit corresponding to the 3,4-ethylenedioxythiophene compound and a second monomer unit corresponding to the 3,4-dialkoxythiophene compound.
  • the precursors are at least one of the oligomers of the 3,4-ethylenedioxythiophene compound and the 3,4-ethylenedioxythiophene compound, and the oligomers of the 3,4-dialkoxythiophene compound and the 3,4-dialkoxythiophene compound.
  • a high capacitance can be ensured in an electrolytic capacitor using a conductive polymer containing a monomer unit corresponding to a 3,4-ethylenedioxythiophene compound.
  • a polymer obtained by polymerizing a 3,4-ethylenedioxythiophene compound such as PEDOT exhibits relatively high conductivity, it is used as a conductive polymer in an electrolytic capacitor including a solid electrolyte layer (conductive polymer layer). ing.
  • electrolytic capacitors using such conductive polymers are required to have a higher capacity.
  • a conductive polymer containing a first monomer unit corresponding to a 3,4-ethylenedioxythiophene compound and a second monomer unit corresponding to a 3,4-dialkoxythiophene compound Use.
  • a conductive polymer By using such a conductive polymer, it is possible to secure a high capacitance as compared with the case where a conventional conductive polymer such as PEDOT is used. Further, the dielectric loss tangent tan ⁇ can be suppressed to a low level, and the quality of the electrolytic capacitor can be further stabilized.
  • the ESR tends to increase when the electrolytic capacitor is exposed to a high temperature.
  • the rate of change in ESR when exposed to a high temperature can be reduced.
  • the coating property by the molecule is enhanced.
  • the conductive polymer layer is formed using a treatment liquid containing a conductive polymer
  • the conductive polymer contains a second monomer unit, so that the pores and pits on the surface of the anode are impregnated. It is considered that the covering property can be improved by increasing the amount.
  • the conductive polymer contains the second monomer unit in addition to the first monomer unit, it is considered that the conductivity of the conductive polymer contained in the capacitor element is improved by increasing the orientation of the conductive polymer. Be done.
  • the conductive polymer contains the first monomer unit and the second monomer unit, the dedoping of the dopant is suppressed and the thermal stability of the conductive polymer is enhanced. As a result, it is considered that the high conductivity of the conductive polymer layer is maintained even after the electrolytic capacitor is exposed to a high temperature.
  • the electrolytic capacitor includes a capacitor element.
  • the electrolytic capacitor may further contain a liquid component.
  • the capacitor element includes at least an anode having a dielectric layer on its surface and a conductive polymer covering a part of the dielectric layer.
  • the anode body can include a valve acting metal, an alloy containing a valve acting metal, a compound containing a valve acting metal, and the like. These materials can be used alone or in combination of two or more.
  • the valve acting metal for example, aluminum, tantalum, niobium, and titanium are preferably used.
  • An anode having a porous surface can be obtained by roughening the surface of a base material (such as a foil-shaped or plate-shaped base material) containing a valve acting metal by etching or the like.
  • the anode body may be a molded body of particles containing a valve acting metal or a sintered body thereof. The sintered body has a porous structure.
  • the dielectric layer is formed by anodizing the valve acting metal on the surface of the anode body by chemical conversion treatment or the like.
  • the dielectric layer may be formed so as to cover at least a part of the anode body.
  • the dielectric layer is usually formed on the surface of the anode. Since the dielectric layer is formed on the porous surface of the anode body, it is formed along the inner wall surface of the holes and pits on the surface of the anode body.
  • the dielectric layer contains an oxide of the valvening metal.
  • the dielectric layer when tantalum is used as the valve acting metal contains Ta 2 O 5
  • the dielectric layer when aluminum is used as the valve acting metal contains Al 2 O 3 .
  • the dielectric layer is not limited to this, and may be any one that functions as a dielectric.
  • the dielectric layer is formed along the surface of the anode, including the inner walls of holes and pits.
  • the conductive polymer adheres so as to cover a part of the dielectric layer to form the conductive polymer layer.
  • the conductive polymer constitutes at least a part of the cathode body in the electrolytic capacitor.
  • the conductive polymer layer may further contain at least one of a dopant and an additive, if desired.
  • a polymer containing a first monomer unit corresponding to the 3,4-ethylenedioxythiophene compound and a second monomer unit corresponding to the 3,4-dialkoxythiophene compound is used as the conductive polymer.
  • Examples of the 3,4-ethylenedioxythiophene compound include EDOT or a substituent thereof (specifically, EDOT having a substituent (first substituent)).
  • Examples of the first substituent include a hydrocarbon group (alkyl group (C 1-4 alkyl group (methyl group, ethyl group, etc.), etc.), cycloalkyl group, aryl group, aralkyl group, etc.), alkoxy group (C 1).
  • Alkoxy group (methoxy group, ethoxy group, etc.), alkylthio group, carbonyl group, thiocarbonyl group, sulfoxide group, sulfonic acid group, sulfonate group, amino group, formyl group, carboxylic acid ester group (acyloxy group, alkoxy group) Carbonyl group, etc.), acyl group, carboxy group, carbonate group, cyano group, alkylsilyl group, alkoxysilyl group, carboxylic acid amide group (acylamino group, etc.) and the like.
  • the EDOT may have one or more of these substituents. When the EDOT has a substituent, at least one of an alkyl group and an alkoxy group is preferable among these substituents.
  • the conductive polymer may contain one type of first monomer unit, or may contain two or more types.
  • Examples of the 3,4-dialkoxythiophene compound include 3,4-dialkoxythiophene.
  • Examples of the alkoxy group contained in the 3,4-dialkoxythiophene compound include C 1-4 alkoxy group, which may be C 1-3 alkoxy group or C 1-2 alkoxy group.
  • the alkoxy group may be either linear or branched. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group.
  • the alkoxy groups at the 3- and 4-positions of the thiophene ring may be the same or different.
  • the conductive polymer may contain one type of second monomer unit, or may contain two or more types.
  • the amount of the second monomer unit in the conductive polymer is, for example, 0.005 parts by mass or more and 15 parts by mass or less, and 0.008 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first monomer unit. There may be. When the amount of the second monomer unit is in such a range, a higher capacitance is likely to be obtained. From the viewpoint of obtaining lower dielectric loss tangent tan ⁇ and ESR, the amount of the second monomer unit is preferably 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the first monomer unit.
  • the conductive polymer may contain a third monomer unit other than the first monomer unit and the second monomer unit.
  • the total molar ratio of the first monomer unit and the second monomer unit in the conductive polymer is preferably 90 mol% or more.
  • the total molar ratio of the first monomer unit and the second monomer unit in the conductive polymer is 100 mol% or less.
  • the dopant for example, at least one selected from the group consisting of anions and polyanions is used.
  • anion examples include sulfate ion, nitrate ion, phosphate ion, borate ion, organic sulfonic acid ion, carboxylic acid ion, etc., but are not particularly limited.
  • dopants that generate sulfonic acid ions include paratoluenesulfonic acid and naphthalenesulfonic acid.
  • polyanion examples include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and poly.
  • Acrylic acid can be mentioned. These may be used alone or in combination of two or more. Further, these may be polymers of a single monomer or may be a copolymer of two or more kinds of monomers. Of these, a polyanion derived from polystyrene sulfonic acid is preferable.
  • the conductive polymer layer may be a single layer or may be composed of a plurality of layers.
  • the composition of the conductive polymer contained in each layer may be the same or different.
  • a metal foil may be used for the cathode body as well as the anode body.
  • the type of metal is not particularly limited, but it is preferable to use a valve acting metal such as aluminum, tantalum, niobium, or an alloy containing a valve acting metal. If necessary, the surface of the metal foil may be roughened.
  • a chemical conversion film may be provided on the surface of the metal foil, or a metal (dissimilar metal) or non-metal film different from the metal constituting the metal foil may be provided. Examples of dissimilar metals and non-metals include metals such as titanium and non-metals such as carbon.
  • a separator When the metal foil is used as the cathode body, a separator may be arranged between the metal foil and the anode body.
  • the separator is not particularly limited, and for example, a non-woven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (for example, aromatic polyamide such as aliphatic polyamide and aramid) may be used.
  • the electrolytic capacitor may be a wound type, a chip type, or a laminated type.
  • the configuration of the capacitor element may be selected according to the type of electrolytic capacitor.
  • the electrolytic capacitor contains a liquid component, it is advantageous in ensuring a higher capacitance. Further, the ESR change rate after exposing the electrolytic capacitor to a high temperature can be further reduced.
  • the liquid component contains a solvent.
  • the solvent include sulfone compounds, lactone compounds, carbonate compounds, polyhydric alcohols and the like.
  • the solvent one type may be used, or two or more types may be used in combination.
  • Examples of the sulfone compound include sulfolane, dimethyl sulfoxide and diethyl sulfoxide.
  • Examples of the lactone compound include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, fluoroethylene carbonate and the like.
  • a liquid component containing a polyhydric alcohol containing a polyhydric alcohol.
  • the ratio of the polyhydric alcohol to the total solvent contained in the liquid component is, for example, 50% by mass or more, and may be 75% by mass or more or 90% by mass or more.
  • the ratio of the polyhydric alcohol to the total solvent contained in the liquid component is 100% by mass or less.
  • polyhydric alcohol examples include glycerin compounds, sugar alcohol compounds, glycol compounds and the like.
  • Examples of the glycerin compound include glycerin, polyglycerin (diglycerin, triglycerin, etc.), and derivatives thereof.
  • the number of repetitions of the glycerin unit in polyglycerin is, for example, 2 or more and 20 or less, and may be 2 or more and 10 or less.
  • Examples of the sugar alcohol compound include sugar alcohols (erythritol, mannitol, pentaerythritol, etc.) or derivatives thereof.
  • Examples of the derivative include an alkylene oxide adduct (such as glycerin, polyglycerin, or an adduct in which one alkylene oxide is added to one hydroxy group of a sugar alcohol).
  • Examples of the alkylene oxide adduct include a C 2-4 alkylene oxide adduct (such as an ethylene oxide adduct).
  • Glycol compounds include alkylene glycol (C 2-4 alkylene glycol (ethylene glycol, propylene glycol, etc.), etc.), polyalkylene glycol (poly C 2-4 alkylene glycol (diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, etc.), etc. ) Etc.), polyalkylene oxide adducts of sugar alcohols (glycerin, erythritol, mannitol, pentaerythritol, etc.) (poly C 2-4 alkylene oxide adducts (polyethylene oxide adduct, etc.), etc.) and the like.
  • the weight average molecular weight (Mw) of the polyalkylene oxide adduct of polyalkylene glycol or sugar alcohol is, for example, 150 or more and 3000 or less, and may be 200 or more and 1000 or less.
  • Mw is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). GPC is usually measured using a polystyrene gel column and water / methanol (volume ratio 8/2) as a mobile phase.
  • the liquid component may contain a solute.
  • solute include an acid component and a base component.
  • the acid component examples include carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids (including polyvalent carboxylic acids such as phthalic acid and pyromellitic acid)) and sulfur-containing acids (sulfuric acid, sulfonic acid (aliphatic sulfone)).
  • carboxylic acids aliphatic carboxylic acids, aromatic carboxylic acids (including polyvalent carboxylic acids such as phthalic acid and pyromellitic acid)
  • sulfur-containing acids sulfuric acid, sulfonic acid (aliphatic sulfone)
  • a condensate of a carboxylic acid and an inorganic acid (boric acid, phosphoric acid, etc.) (borodisalicylic acid, borodiglycolic acid, borodishuic acid, etc.) may be used.
  • Aromatic sulfonic acids include aromatic sulfonic acids having a hydroxy group or a carboxy group (oxyaromatic sulfonic acid (for example, phenol-2-sulfonic acid)) and sulfoaromatic carboxylic acid (for example, p-sulfobenzoic acid) in addition to the sulfo group. Acids, 3-sulfophthalic acid, 5-sulfosalicylic acid), etc.) are also included.
  • the liquid component may contain one kind of acid component, or may contain two or more kinds.
  • Examples of the base component include ammonia, amines (specifically, primary amines, secondary amines, and tertiary amines), quaternary ammonium compounds, and amidinium compounds.
  • the amine may be any of an aliphatic, aromatic, and heterocyclic formula. Examples of the amine include trimethylamine, diethylamine, triethylamine, ethylenediamine, aniline, pyrrolidine, imidazole, 4-dimethylaminopyridine and the like. Examples of the quaternary ammonium compound include amidine compounds (including imidazole compounds).
  • the liquid component may contain one kind of base component, or may contain two or more kinds.
  • the liquid component may contain an acid component and a base component in a free state, or may be contained in the form of a salt.
  • the liquid component may contain an organic salt. Examples of the organic salt include those in which at least one of an acid component and a base component is organic.
  • the pH of the liquid component is preferably 4 or less, and may be 3.8 or less, or 3.6 or less. When the pH of the liquid component is in such a range, deterioration of the conductive polymer is likely to be suppressed.
  • the pH is preferably 1.0 or higher.
  • the concentration of the solute in the liquid component is, for example, 0.1% by mass or more and 25% by mass or less, and may be 0.5% by mass or more and 15% by mass or less. When the concentration of the solute is in such a range, the dedoping of the dopant is likely to be suppressed.
  • FIG. 1 is a schematic cross-sectional view of the electrolytic capacitor according to the present embodiment
  • FIG. 2 is a schematic view of a part of the capacitor element related to the electrolytic capacitor.
  • Electrolytic capacitors include, for example, a capacitor element 10, a bottomed case 101 that houses the capacitor element 10 and a liquid component (not shown), a sealing body 102 that closes the opening of the bottomed case 101, and a seat plate that covers the sealing body 102.
  • the 103 is provided with lead wires 104A and 104B derived from the sealing body 102 and penetrating the seat plate 103, and lead tabs 105A and 105B for connecting the lead wire and the electrode of the capacitor element 10.
  • the vicinity of the open end of the bottomed case 101 is drawn inward, and the open end is curled so as to be crimped to the sealing body 102.
  • the capacitor element 10 is, for example, a wound body as shown in FIG.
  • the winding body includes an anode body 11 connected to the lead tab 105A, a cathode body 12 connected to the lead tab 105B, and a separator 13.
  • a conductive polymer layer (not shown) is formed on the anode body 11. Then, at least the conductive polymer layer of the capacitor element 10 may be impregnated with a liquid component.
  • FIG. 2 shows a partially unfolded state before stopping the outermost circumference of the winding body.
  • the electrolytic capacitor may have at least one capacitor element, and may have a plurality of capacitor elements.
  • the number of capacitor elements included in the electrolytic capacitor may be determined according to the application.
  • the electrolytic capacitor is manufactured by a manufacturing method including at least a step of preparing an anode, a step of forming a dielectric layer, and a step of treating the anode with a treatment liquid containing a conductive polymer or a precursor thereof. NS.
  • a metal foil formed of a valve acting metal is used as the raw material of the anode body 11.
  • the surface of the metal foil is roughened by etching or the like, and a plurality of irregularities are formed on the surface of the metal foil. In this way, the anode body 11 is prepared.
  • a dielectric layer is formed on the surface of the roughened metal foil by chemical conversion treatment or the like.
  • Step of preparing the cathode body 12 As the raw material of the cathode body 12, a metal foil formed of a valve acting metal is used. The surface of the cathode body 12 may be roughened, if necessary.
  • the anode body 11 and the cathode body 12 are wound around the separator 13 to prepare a wound body.
  • the winding stop tape 14 is arranged on the outer surface of the cathode body 12 located on the outermost layer of the winding body, and the end portion of the cathode body 12 is fixed. If necessary, the wound body is further subjected to chemical conversion treatment.
  • Step of treating the anode 11 with a treatment liquid (third step)
  • the treatment liquid containing the conductive polymer or its precursor can be brought into contact with at least the dielectric layer.
  • the treatment liquid is brought into contact with at least the dielectric layer by immersing the anode body on which the dielectric layer is formed in the treatment liquid or injecting the treatment liquid into the anode body on which the dielectric layer is formed. Can be made to.
  • a conductive polymer film covering at least a part of the dielectric layer is formed.
  • a capacitor element 10 in which a conductive polymer is arranged between the anode body 11 and the cathode body 12 can be obtained.
  • a treatment liquid containing a precursor of a conductive polymer When a treatment liquid containing a precursor of a conductive polymer is used, it is preferable to immerse the anode and polymerize the precursor by chemical polymerization or electrolytic polymerization to produce a conductive polymer.
  • the anode is usually dried after being removed from the treatment solution. When drying, the anode may be heated if necessary. The anode body taken out from the treatment liquid may be washed if necessary prior to drying. In this way, the conductive polymer layer is formed.
  • the treatment liquid is brought into contact with at least the dielectric layer of the anode and dried. In this way, the conductive polymer layer is formed.
  • the anode may be heated if necessary.
  • the treatment liquid is prepared by dissolving or dispersing the components of the treatment liquid in a liquid medium.
  • Constituents include, for example, conductive polymers or precursors thereof, dopants, additives and the like.
  • the description about the conductive polymer layer can be referred to.
  • Examples of the precursor of the conductive polymer include monomers and oligomers (including prepolymers) of the conductive polymer.
  • the treatment liquid may contain one kind of precursor, or may contain two or more kinds of precursors.
  • the precursors are at least one of the 3,4-ethylenedioxythiophene compound (first monomer) and its oligomer (first oligomer), and the 3,4-dialkoxythiophene compound (second monomer) and its oligomer (second monomer). It may contain at least one of the oligomers).
  • the precursor may contain an oligomer (third oligomer) containing a first monomer unit and a second monomer unit.
  • the precursor may include a third oligomer and at least one selected from the group consisting of a first monomer, a first oligomer, a second monomer, and a second oligomer.
  • a third oligomer and at least one selected from the group consisting of a first monomer, a first oligomer, a second monomer, and a second oligomer.
  • the description about the conductive polymer layer can be referred to.
  • the ratio of each monomer or oligomer in the precursor may be determined so that the amount of the second monomer unit with respect to 100 parts by mass of the first monomer unit in the conductive polymer is within the above range.
  • the amount of the second monomer with respect to 100 parts by mass of the first monomer is described as the amount of the second monomer unit with respect to 100 parts by mass of the first monomer unit. It may be a range.
  • Examples of the liquid medium contained in the treatment liquid include water, an organic medium, and a mixture thereof.
  • Examples of the organic medium include aliphatic alcohols, aliphatic ketones (acetone and the like), nitriles (acetonitrile and the like), amides (N, N-dimethylformamide and the like), sulfoxides (dimethyl sulfoxide and the like) and the like.
  • As the aliphatic alcohol an aliphatic alcohol having 1 to 5 carbon atoms is preferable.
  • the aliphatic alcohol may be either monool or polyol. Aliphatic monools include, for example, methanol, ethanol, propanol, butanol.
  • Examples of the aliphatic polyol include ethylene glycol and glycerin.
  • the treatment liquid can contain known additives used when forming the conductive polymer layer.
  • a silane compound may be used as the additive.
  • an oxidizing agent is used to polymerize the precursor.
  • the oxidizing agent may be contained in the treatment liquid as an additive. Further, the oxidizing agent may be applied to the anode body before or after the treatment liquid is brought into contact with the anode body on which the dielectric layer is formed. Examples of such an oxidizing agent include sulfates, sulfonic acids, and salts thereof.
  • the oxidizing agent may be used alone or in combination of two or more.
  • sulfates include salts of ferric sulfate, sulfuric acid such as sodium persulfate, sulfuric acids such as persulfuric acid, and metals.
  • the metal constituting the salt include alkali metals (sodium, potassium, etc.), iron, copper, chromium, zinc, and the like.
  • the sulfonic acid or a salt thereof has a function as a dopant in addition to a function as an oxidizing agent.
  • a small molecule sulfonic acid or a salt thereof exemplified for the dopant is used as the sulfonic acid or a salt thereof.
  • the step of forming the conductive polymer layer by immersion in the treatment liquid and polymerization (or drying) may be performed once or may be repeated a plurality of times. Conditions such as the composition and viscosity of the treatment liquid may be the same each time, or at least one condition may be changed.
  • (V) Liquid component impregnation step In this step, the capacitor element 10 may be impregnated with a liquid component. As a result, an electrolytic capacitor having a conductive polymer and a liquid component can be obtained. This step is performed after the third step.
  • the liquid component may be impregnated into the capacitor element 10 by accommodating the capacitor element 10 and the liquid component in a container, or may be impregnated by immersing the capacitor element 10 in the liquid component. May be impregnated by dropping a liquid component into the capacitor.
  • the liquid component is prepared prior to this step.
  • the liquid component can be prepared by mixing the constituent components.
  • Step of Sealing the Capacitor Element 10 The capacitor element 10 is housed in the bottomed case 101 so that the lead wires 104A and 104B are located on the opening side of the bottomed case 101.
  • the bottomed case 101 also contains a liquid component.
  • the opening of the bottomed case 101 is closed with the sealing body 102 through which each lead wire penetrates, the opening end is crimped to the sealing body 102 and curled, and the seat plate 103 is arranged in the curled portion.
  • An electrolytic capacitor as shown in is completed.
  • the winding type electrolytic capacitor has been described, but the scope of application of the present invention is not limited to the above, and other electrolytic capacitors, for example, chip type electrolysis using a metal sintered body as an anode body. It can also be applied to capacitors and laminated electrolytic capacitors that use a metal plate as an anode.
  • An aluminum foil having a thickness of 100 ⁇ m was etched to roughen the surface of the aluminum foil. Then, a dielectric layer was formed on the surface of the aluminum foil by chemical conversion treatment. The chemical conversion treatment was carried out by immersing an aluminum foil in an ammonium adipate solution and applying a voltage of 180 V to the aluminum foil. Then, the aluminum foil was cut to prepare an anode body.
  • the anode lead tab and the cathode lead tab were connected to the anode body and the cathode body, and the anode body and the cathode body were wound through the separator while involving the lead tab.
  • An anode lead wire and a cathode lead wire were connected to the end of each lead tab protruding from the winding body.
  • the produced wound body was subjected to chemical conversion treatment again to form a dielectric layer at the cut end of the anode body.
  • the end portion of the outer surface of the winding body was fixed with a winding stop tape to prepare a winding body.
  • Iron (III) sulfate (oxidizing agent) dissolved in ion-exchanged water was added while stirring the mixed solution, and the polymerization reaction was carried out. After the reaction, the resulting reaction was dialyzed to remove unreacted monomers and excess oxidant, and the first monomer unit (and optionally the second monomer unit or second) doped with about 5% by weight PSS. A polymer dispersion containing a polymer containing (3 monomer units) was obtained.
  • the electrolytic capacitor of the present disclosure can be used as a solid electrolytic capacitor or a hybrid electrolytic capacitor. Electrolytic capacitors are also suitable for applications that require high heat resistance. However, the applications of electrolytic capacitors are not limited to these.
  • Electrolytic capacitor 101 Bottomed case 102: Sealing body 103: Seat plate 104A, 104B: Lead wire 105A, 105B: Lead tab 10: Capacitor element 11: Anode body 12: Cathode body 13: Separator 14: Winding tape

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JP2012142373A (ja) * 2010-12-28 2012-07-26 Japan Carlit Co Ltd:The 固体電解コンデンサ及びその製造方法
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