WO2023008288A1 - 電解コンデンサ - Google Patents

電解コンデンサ Download PDF

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Publication number
WO2023008288A1
WO2023008288A1 PCT/JP2022/028246 JP2022028246W WO2023008288A1 WO 2023008288 A1 WO2023008288 A1 WO 2023008288A1 JP 2022028246 W JP2022028246 W JP 2022028246W WO 2023008288 A1 WO2023008288 A1 WO 2023008288A1
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Prior art keywords
component
acid
anion
electrolytic capacitor
anion component
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English (en)
French (fr)
Japanese (ja)
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博之 有馬
穂南 児島
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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 CN202280050833.1A priority Critical patent/CN117678042A/zh
Priority to JP2023538469A priority patent/JP7836953B2/ja
Priority to US18/580,619 priority patent/US12444549B2/en
Publication of WO2023008288A1 publication Critical patent/WO2023008288A1/ja
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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
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • H01G9/022—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
    • H01G9/145—Liquid electrolytic capacitors
    • 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

  • This disclosure relates to electrolytic capacitors.
  • Electrolytic capacitors which are equipped with a capacitor element containing a conductive polymer and an electrolytic solution, are considered promising as capacitors that are small, have a large capacity, and have a low ESR (equivalent series resistance).
  • a liquid component such as a non-aqueous solvent or a solution obtained by dissolving a solute in a non-aqueous solvent is used.
  • Patent Document 1 proposes using an electrolytic solution containing a solvent containing a glycol compound and a solute containing an acid component and a base component in an electrolytic capacitor.
  • the solute contains more acid components than base components by weight, and the acid components contain hydroxy-bearing aromatic compounds.
  • Patent document 2 proposes the use of a driving electrolyte consisting of an organic solvent, a solute, and an additive in an electrolytic capacitor.
  • the solute is composed of an acid component material and a base component material
  • the acid component material has an organic carboxylic acid such as phthalic acid and an inorganic acid such as boric acid, and the acid component is more than the base component. A molar excess is described.
  • An electrolytic capacitor includes a capacitor element containing a conductive polymer and a liquid component.
  • the liquid component includes a first anion component having a carbonyloxy bond and a second anion component having no carbonyloxy bond and a sulfonylimide bond.
  • FIG. 1 is a cross-sectional schematic diagram of an electrolytic capacitor according to an embodiment of the present disclosure
  • FIG. 2 is a schematic diagram for explaining the configuration of a capacitor element in FIG. 1;
  • the film repairability of the dielectric layer may decrease, or the conductivity of the conductive polymer may decrease. Therefore, it is difficult to maintain a low equivalent series resistance (ESR) and ensure stable capacitor performance.
  • ESR equivalent series resistance
  • Carboxylic acid such as phthalic acid is sometimes used as an anion component in the liquid component of an electrolytic capacitor having a capacitor element containing a conductive polymer.
  • Carboxylic acid exhibits an appropriate pH, so it has the effect of chemically converting the anode body, and is excellent in film repairability, so that the effect of suppressing leakage current is maintained.
  • the conductivity of the molecule fluctuates and the ESR fluctuates.
  • An anionic component with a lower pH than the carboxyl group such as sulfonic acid or its derivatives, may be used as the liquid component.
  • the pH of the liquid component becomes low, it is easy to maintain the high conductivity of the conductive polymer, so it is easy to keep the ESR low.
  • an anionic component with a low pH is used, the anode body is oxidized excessively, degrading the film repairability, and the electrodes and the like are likely to be corroded, resulting in degraded capacitor performance.
  • the electrolytic capacitor of the present disclosure uses a liquid component containing a first anion component having a carbonyloxy bond and a second anion component having no carbonyloxy bond and having a sulfonylimide bond.
  • a liquid component containing a first anion component having a carbonyloxy bond and a second anion component having no carbonyloxy bond and having a sulfonylimide bond.
  • liquid component contains the first anion component and the second anion component, and usually contains a solvent.
  • the liquid component may contain other anion components (third anion component), cationic components, additives, etc., as necessary.
  • the first anion component includes an acid having a carbonyloxy bond and an anionic derivative of an acid having a carbonyloxy bond.
  • acids having a carbonyloxy bond examples include carboxylic acid, oxocarbonic acid, and Meldrum's acid.
  • Oxocarboxylic acids include delta acid, squaric acid, croconic acid, rhodizonic acid, heptagonic acid and the like.
  • carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids.
  • Acids with a carbonyloxy bond also include sulfoaromatic carboxylic acids.
  • Sulfoaromatic carboxylic acids include p-sulfobenzoic acid, 3-sulfophthalic acid, 5-sulfosalicylic acid and the like.
  • aromatic carboxylic acids are preferred because of their high stability.
  • benzoic acid, phthalic acid, pyromellitic acid, salicylic acid, and the like can be used as the aromatic carboxylic acid.
  • phthalic acid, salicylic acid, and benzoic acid are preferred.
  • hydroxy acid and polycarboxylic acid are preferable.
  • Hydroxy acids include aliphatic hydroxy acids (glycolic acid, lactic acid, tartronic acid, hydroxybutyric acid, malic acid, citric acid, etc.), aromatic hydroxy acids (salicylic acid, hydroxybenzoic acid, mandelic acid, benzilic acid, gallic acid, etc.).
  • polycarboxylic acids include aliphatic polycarboxylic acids (oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, etc.) and aromatic polycarboxylic acids (phthalic acid, etc.).
  • Derivatives include, for example, acid coordination compounds having a carbonyloxy bond.
  • Such coordination compounds include, for example, coordination compounds in which at least one central atom selected from the group consisting of boron, aluminum and silicon and an acid having a carbonyloxy bond are bonded to this central atom.
  • the coordination compound can have a structure in which at least the oxy group of the carbonyloxy bond of the acid is coordinated to the central atom.
  • the coordination compound may have a structure in which each of the oxy groups of at least two carbonyloxy bonds is coordinated to the central atom.
  • the coordination compound may have a structure in which an oxygen atom derived from the hydroxy group and an oxy group of a carbonyloxy bond are coordinated to the central atom.
  • coordination compounds include, but are not limited to, borodisalicylic acid, borodisoxalic acid, borodisalicylic acid, and borodisaligal acid.
  • the liquid component may contain one kind of the first anion component, or may contain two or more kinds in combination.
  • first anion components phthalic acid, salicylic acid, benzoic acid, borodisalicylic acid, borodisalicylic acid, borodisalicylic acid (especially phthalic acid, salicylic acid, and borodisalicylic acid) are preferred.
  • the anionic group of the first anion component may be contained in any form such as anion such as carboxy anion (-COO - ), free acid (-COOH etc.), and salt.
  • the coordination compound may exhibit anionic properties while the carbonyloxy bond is coordinated to the central atom. Including these forms may be referred to as an anionic group.
  • Such second anionic component is capable of forming a sulfonylimide anion.
  • the second anion component may have a cyclic structure containing a sulfonylimide bond, or may have a chain structure.
  • the cyclic structure may be condensed with an aromatic ring or the like. At least one of the sulfonyl group and the imide group may have a ring (aromatic ring, aliphatic ring, heterocyclic ring, etc.).
  • the second anion component examples include saccharin (pKa: 1.6), 1,2-benzenedisulfonimide (pKa: -1.1), and cyclohexafluoropropane-1,3-bis(sulfonyl)imide.
  • the acid dissociation constant pKa of the second anion component in the form of free acid is preferably 5.0 or less from the viewpoint of high effect of stably maintaining the pH of the liquid component at a low state.
  • the pKa is 5.0 or less, the second anion component is likely to dissociate, easily lowering the pH of the liquid component.
  • the pH of the liquid component is low, dedoping is less likely to occur and the high conductivity of the conductive polymer can be stably maintained.
  • the pH of the liquid component is too low, metal parts (eg, electrodes) in contact with the liquid component in the electrolytic capacitor may corrode.
  • the pKa of the second anion in the free acid form is preferably higher than -2.0, more preferably -1.0 or higher.
  • the acid dissociation constant means the acid dissociation constant in water at a temperature of 25°C.
  • the anionic component in the free acid form exhibits multiple pKas, it means the highest pKa (ie, pKa 1 ).
  • the pKa of the second anion component in the free acid form is adjusted, for example, by adjusting the distribution of electrons in the imide group of the sulfonylimide group. For example, when an electron-donating group such as a phenyl group or a tolyl group is bound to the imide group, the pKa tends to be high. When a sulfonyl group is bonded to one bond of the imide group and the other is bonded to an electron-withdrawing group such as a sulfonyl group or a carbonyl group, the pKa tends to be low.
  • Either an electron-donating group or an electron-withdrawing group may be attached to the sulfonyl group attached to the imide group.
  • the pKa tends to be lower.
  • a hydrocarbon group having a fluorine atom such as a fluoroalkyl group
  • the effect of reducing pKa is enhanced. It is preferable to select the second anion component in consideration of these factors.
  • a sulfonyl group and a carbonyl group or to at least one of the two sulfonyl groups is preferred a second anionic component in which an electron-donating group is bound.
  • a second anion component having an electron-withdrawing group bonded to the sulfonyl group is preferred.
  • saccharin pKa: 1.6
  • 4-methyl-N-[(4-methylphenyl)sulfonyl]benzenesulfonamide pKa: -0.0
  • pKa 4-methyl-N-[(4-methylphenyl)sulfonyl]benzenesulfonamide
  • pKa: 4.35 trifluoromethanesulfonanilide
  • the liquid component may contain one type of the second anion component, or may contain two or more types in combination.
  • the amount of the second anion component is preferably 3 parts by mass or more, more preferably 5 parts by mass or more (or 10 parts by mass or more) with respect to 100 parts by mass of the first anion component.
  • the amount of the second anion component is within such a range, even if the first anion component disappears due to a side reaction or the like, the pH of the liquid component can be easily kept low, and the decrease in conductivity of the conductive polymer can be reduced. easy.
  • the amount of the second anion component relative to 100 parts by mass of the first anion component is more preferably 12.5 parts by mass or more (or 25 parts by mass or more), and 18 parts by mass or more ( or 35 parts by mass or more) is more preferable.
  • the amount of the second anion component is, for example, 250 parts by mass or less (or 120 parts by mass or less), or 230 parts by mass or less (or 115 parts by mass or less) with respect to 100 parts by mass of the first anion component. It may be 227 parts by mass or less. When the amount of the second anion component is within such a range, the effect of repairing the film of the dielectric layer by the first anion component is likely to be obtained. These upper and lower limits can be combined arbitrarily. However, the amount of each anion component is determined in terms of free acid, not anion or salt.
  • the liquid component may optionally contain an anion component (third anion component) other than the first anion component and the second anion component.
  • the third anion component include phenolic compounds (picric acid, p-nitrophenol, pyrogallol, catechol, etc.), coordination compounds of phenolic compounds (borodicatechol, borodipyrogallol, etc.), sulfur-containing acids (sulfuric acid, sulfone Acid (aromatic sulfonic acid, etc.), oxyaromatic sulfonic acid (phenol-2-sulfonic acid, etc.), boron-containing acid (boric acid, halogenated boric acid (tetrafluoroboric acid, etc.), or partial esters thereof etc.), phosphorus-containing acids (phosphoric acid, halogenated phosphoric acid (hexafluorophosphoric acid, etc.), phosphonic acid, phosphinic acid, or partial esters thereof), nitrogen-containing acids (nitric acid,
  • the third anion component may be contained in the liquid component in the form of an anion, in the free form, or in the form of a salt. All these forms are sometimes referred to as the third anion component.
  • the amount of the third anion component is, for example, 30 parts by mass or less (or 15 parts by mass or less), or 20 parts by mass or less (or 10 parts by mass or less) with respect to 100 parts by mass of the first anion component. good.
  • the liquid component may be 0.1 parts by mass or more with respect to 100 parts by mass of the first anion. It is also preferable if the liquid component does not contain the third anion component.
  • the case where the third anion component is not included includes the case where the third anion component or trace thereof is below the detection limit in the liquid component. However, the amount of the third anion component is determined in terms of the free acid, not the anion or salt.
  • Solvents include sulfone compounds, lactone compounds, carbonate compounds, polyhydric alcohols and the like.
  • the liquid component may contain one type of solvent or a combination of two or more types.
  • Sulfone compounds include sulfolane (SL), dimethylsulfoxide and diethylsulfoxide.
  • Lactone compounds include ⁇ -butyrolactone (GBL), ⁇ -valerolactone and the like.
  • Carbonate compounds include dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate and fluoroethylene carbonate.
  • Polyhydric alcohols include glycerin compounds, sugar alcohol compounds, and glycol compounds.
  • Glycerin compounds include glycerin, polyglycerin (diglycerin, triglycerin, etc.), or derivatives thereof.
  • the number of repeating glycerin units in polyglycerin is, for example, 2 or more and 20 or less, and may be 2 or more and 10 or less.
  • Sugar alcohol compounds include sugar alcohols (erythritol, mannitol, pentaerythritol, etc.) or derivatives thereof.
  • Derivatives include alkylene oxide adducts (such as glycerin, polyglycerin, or adducts in which one alkylene oxide is added to one hydroxy group of sugar alcohol).
  • Alkylene oxide adducts include C 2-4 alkylene oxide adducts (ethylene oxide adducts, etc.).
  • Glycol compounds include alkylene glycol (C 2-4 alkylene glycol (ethylene glycol (EG), propylene glycol, etc.), etc.), polyalkylene glycol (poly C 2-4 alkylene glycol (diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol (PEG), etc.), polyalkylene oxide adducts of sugar alcohols (glycerin, erythritol, mannitol, pentaerythritol, etc.) (poly- C2-4 alkylene oxide adducts (polyethylene oxide adducts, etc.), etc.), etc. mentioned.
  • the weight average molecular weight (Mw) of the polyalkylene glycol or polyalkylene oxide adduct of 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 the cationic component in the form of a cation, in the free form, or in the form of a salt. All these forms are sometimes referred to as cationic components.
  • Examples of cationic components include ammonia, amines (specifically, primary amines, secondary amines and tertiary amines), quaternary ammonium compounds and amidinium compounds.
  • Amines can be aliphatic, aromatic, and heterocyclic.
  • Examples of amines include trimethylamine, diethylamine, ethyldimethylamine, triethylamine, ethylenediamine, aniline, pyrrolidine, imidazole (1,2,3,4-tetramethylimidazolinium, etc.), 4-dimethylaminopyridine and the like.
  • Examples of quaternary ammonium compounds include amidine compounds (including imidazole compounds).
  • the liquid component may contain one type of cationic component, or may contain two or more types in combination.
  • the molar ratio of the total amount of the anionic component to the cationic component may be, for example, 0.5 or more, or may be 1 or more. From the viewpoint of suppressing dedoping and easily ensuring high conductivity of the conductive polymer, it is preferable to use the anion component excessively with respect to the cation component.
  • the molar ratio of the total anionic component to the cationic component is preferably 1.1 or more, and may be 1.5 or more.
  • the molar ratio of the total anionic component to the cationic component is, for example, 50 or less, and may be 20 or less. These lower and upper limits can be combined arbitrarily.
  • the molar ratio of the first anion component to the cation component is preferably 1 or more, more preferably 1.1 or more, and may be 1.5 or more.
  • the above molar ratio is preferably 10 or less, more preferably 5 or less.
  • the total concentration of the anion component and the cation component in the liquid component is, for example, 0.1% by mass or more and 30% by mass or less, and may be 0.5% by mass or more and 25% by mass or less, or 0.5% by mass. It may be more than or equal to 15% by mass or less.
  • the total concentration of the anion component and the cation component is within this range, dedoping of the dopant is likely to be suppressed.
  • the amount of each anion component is converted into a free acid, and the amount of a cationic component is calculated into a free base.
  • the pH of the liquid component is preferably 6 or less, more preferably 4 or less, and may be 3.8 or less, or 3.6 or less. By setting the pH of the electrolytic solution in such a range, deterioration of the conductive polymer component can be easily suppressed.
  • the pH is preferably 1.0 or higher.
  • Infrared absorption spectrum, ultraviolet-visible absorption spectrum, gas chromatograph mass spectrometry, liquid chromatograph mass spectrometry, magnetic resonance spectrum, etc. are used to determine the components contained in the liquid component using the liquid component collected from the electrolytic capacitor. can be identified by The liquid component is preferably collected from the initial electrolytic capacitor.
  • the initial electrolytic capacitor is an electrolytic capacitor after break-in charging and discharging or an unused electrolytic capacitor if it is a commercial product. Quantitative analysis of the components contained in the liquid component can be performed using the calibration curve method or the like in the analysis method described above.
  • capacitor element contains a conductive polymer.
  • a capacitor element usually includes at least an anode body having a dielectric layer on its surface and a conductive polymer covering a portion of the dielectric layer.
  • the anode body can contain a valve action metal, an alloy containing a valve action metal, a compound containing a valve action metal, and the like. These materials can be used singly or in combination of two or more. For example, aluminum, tantalum, niobium, and titanium are preferably used as valve metals.
  • An anode body having a porous surface can be obtained, for example, by roughening the surface of a base material (such as a foil-like or plate-like base material) containing a valve action metal by etching or the like.
  • the anode body may be a molded body of particles containing a valve metal or a sintered body thereof. Note that the sintered body has a porous structure.
  • the dielectric layer is formed by anodizing the valve action 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 part of the anode body.
  • a dielectric layer is usually formed on the surface of the anode body. Since the dielectric layer is formed on the porous surface of the anode body, it is formed along the inner wall surfaces of the holes and depressions (pits) on the surface of the anode body.
  • the dielectric layer contains an oxide of a valve metal.
  • the dielectric layer contains Ta 2 O 5 when tantalum is used as the valve metal, and the dielectric layer contains Al 2 O 3 when aluminum is used as the valve metal.
  • the dielectric layer is not limited to this, and may be any material as long as it functions as a dielectric.
  • the dielectric layer is formed along the surface of the anode body (including the inner walls of the pores).
  • a conductive polymer includes, for example, a conjugated polymer and a dopant.
  • a conductive polymer is attached so as to cover a portion of the dielectric layer.
  • the conductive polymer adhered to the surface of the dielectric layer may constitute a layer.
  • Conductive polymers are sometimes called solid electrolytes.
  • the conductive polymer constitutes at least part of the cathode body in the electrolytic capacitor.
  • the conductive polymer may further contain additives as needed.
  • Conjugated polymers include known conjugated polymers used in electrolytic capacitors, such as ⁇ -conjugated polymers.
  • Conjugated polymers include, for example, polymers having polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylenevinylene, polyacene, and polythiophenevinylene as a basic skeleton.
  • the above polymer may contain at least one type of monomer unit that constitutes the basic skeleton.
  • the above polymers also include homopolymers, copolymers of two or more monomers, and derivatives thereof (substituents having substituents, etc.).
  • polythiophenes include poly(3,4-ethylenedioxythiophene) and the like.
  • Conjugated polymers may be used singly or in combination of two or more.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited, but is, for example, 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight (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.
  • dopant examples include relatively low-molecular-weight anions and polymeric anions. Examples of anions include sulfate, nitrate, phosphate, borate, organic sulfonate, carboxylate and the like. Compounds that generate these anions are used as dopants. Dopants that generate sulfonate ions include, for example, paratoluenesulfonic acid and naphthalenesulfonic acid.
  • polymeric anions examples include polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyester sulfonic acids (such as aromatic polyester sulfonic acids), phenolsulfonic acid novolak resins and polyacrylic acids.
  • the polymeric anion may be a polymer of a single monomer, a copolymer of two or more monomers, or a substituent having a substituent. Among them, polyanions derived from polystyrene sulfonic acid are preferred.
  • dopants are merely examples and are not limited to these.
  • a dopant may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the conductive polymer can be formed, for example, by chemically and/or electrolytically polymerizing a conjugated polymer precursor on the dielectric layer in the presence of a dopant. Alternatively, it can be formed by bringing a solution in which a conductive polymer is dissolved or a dispersion in which a conductive polymer is dispersed into contact with the dielectric layer.
  • the conductive polymer used in these solutions or dispersions can be obtained by polymerizing a conjugated polymer precursor in the presence of a dopant.
  • precursors of conjugated polymers include starting monomers for conjugated polymers, oligomers and prepolymers in which a plurality of molecular chains of starting monomers are linked. One type of precursor may be used, or two or more types may be used in combination.
  • the amount of the dopant contained in the conductive polymer is, for example, 10 to 1000 parts by mass, and may be 20 to 500 parts by mass or 50 to 200 parts by mass with respect to 100 parts by mass of the conjugated polymer.
  • a metal foil may be used for the cathode body as well as for the anode body.
  • the type of metal is not particularly limited, it is preferable to use a valve-acting metal such as aluminum, tantalum, or niobium, or an alloy containing a valve-acting metal. If necessary, the surface of the metal foil may be roughened.
  • the surface of the metal foil may be provided with a chemical conversion coating, or may be provided with a coating of a metal (dissimilar metal) different from the metal constituting the metal foil (dissimilar metal) or a non-metal coating. Examples of dissimilar metals and non-metals include metals such as titanium and non-metals such as carbon.
  • a separator When a 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 nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (eg, aromatic polyamide such as aliphatic polyamide and aramid) may be used.
  • the electrolytic capacitor may be of wound type, chip type or laminated type.
  • An electrolytic capacitor may have at least one capacitor element, and may have a plurality of capacitor elements.
  • an electrolytic capacitor may comprise a stack of two or more capacitor elements, or may comprise two or more wound capacitor elements. The configuration or number of capacitor elements may be selected according to the type or application of the electrolytic capacitor.
  • the electrolytic capacitor of the present disclosure will be described more specifically based on the embodiments.
  • the electrolytic capacitor of the present disclosure is not limited to the following embodiments.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to this embodiment
  • FIG. 2 is a schematic diagram showing a part of a capacitor element of the same electrolytic capacitor.
  • the electrolytic capacitor shown in FIG. 1 includes a capacitor element 10, a bottomed case 11 that accommodates the capacitor element 10, a sealing member 12 that closes an opening of the bottomed case 11, a seat plate 13 that covers the sealing member 12, Lead wires 14A and 14B lead out from sealing member 12 and pass through seat plate 13, lead tabs 15A and 15B connecting the lead wires and electrodes of capacitor element 10, and a liquid component (not shown).
  • the open end of the bottomed case 11 is curled so as to be crimped to the sealing member 12 .
  • the capacitor element 10 is produced from a wound body as shown in FIG.
  • the wound body is a semi-finished product of the capacitor element 10 in which no conductive polymer is arranged between the anode body 21 and the cathode body 22 having dielectric layers on their surfaces.
  • the wound body is obtained by winding the anode body 21 connected to the lead tab 15A and the cathode body 22 connected to the lead tab 15B with the separator 23 interposed therebetween.
  • the outermost circumference of the wound body is fixed by a winding stop tape 24 .
  • FIG. 2 shows a partially unfolded state before the outermost circumference of the wound body is fixed.
  • the anode body 21 has a metal foil with a roughened surface, and a dielectric layer is formed on the roughened surface.
  • Capacitor element 10 is formed by depositing a conductive polymer on at least a portion of the surface of the dielectric layer.
  • Capacitor element 10 is housed in an exterior case together with a liquid component (not shown).
  • Step of Preparing Anode Body 21 and Cathode Body 22 Having Dielectric Layers A metal foil made of a valve metal is used as a raw material for anode body 21 and cathode body 22 .
  • the surface of the metal foil is roughened by etching or the like to form a plurality of irregularities on the surface of the metal foil.
  • a dielectric layer is formed on the roughened surface of the metal foil by chemical conversion treatment or the like. If necessary, the surface of the cathode body 22 may be roughened.
  • capacitor element 10 in which conductive polymer is arranged between anode body 21 and cathode body 22 is obtained.
  • the step of applying the liquid mixture to the surface of the dielectric layer may be repeated two or more times.
  • Step of impregnating the liquid component Prior to the impregnation with the liquid component the liquid component is prepared.
  • the liquid component is prepared by dissolving an anionic component and optionally a cationic component or additives in a solvent.
  • a capacitor element having a conductive polymer is impregnated with the prepared liquid component.
  • a specific impregnation method is not particularly limited. For example, immersion, infusion, or the like may be used.
  • Capacitor element 10 is housed in bottomed case 11 together with a liquid component so that lead wires 14A and 14B are positioned on the opening side of bottomed case 11 .
  • the opening of the bottomed case 11 is closed with a sealing member 12 through which each lead wire passes, the opening end is crimped to the sealing member 12 to be curled, and the seat plate 13 is arranged on the curled portion, as shown in FIG.
  • An electrolytic capacitor as shown in is completed.
  • a wound type electrolytic capacitor has been described, but the scope of application of the present invention is not limited to the above. It can also be applied to capacitors and laminated electrolytic capacitors using a metal plate as an anode.
  • a wound electrolytic capacitor ( ⁇ (diameter) 8 mm ⁇ L (length) 10 mm) having a rated voltage of 35 V and a rated capacitance of 150 ⁇ F was produced.
  • a specific manufacturing method of the electrolytic capacitor will be described below.
  • An aluminum foil having a thickness of 100 ⁇ m was subjected to an etching treatment to roughen the surface of the aluminum foil. After that, 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 60 V thereto. After that, the aluminum foil was cut to prepare an anode body.
  • An anode lead tab and a cathode lead tab were connected to the anode body and the cathode body, and the anode body and the cathode body were wound via a separator while winding the lead tab.
  • An anode lead wire and a cathode lead wire were connected to the ends of each lead tab protruding from the wound body.
  • the produced wound body was subjected to chemical conversion treatment again to form a dielectric layer on the cut end of the anode body. Next, the ends of the outer surface of the wound body were fixed with a winding stop tape to produce a wound body.
  • a mixed solution was prepared by dissolving 3,4-ethylenedioxythiophene (EDOT) and polystyrene sulfonic acid (PSS, weight average molecular weight of 100,000) as a dopant in ion-exchanged water. While stirring the mixed solution, iron (III) sulfate (oxidizing agent) dissolved in ion-exchanged water was added to carry out a polymerization reaction. After the reaction, the obtained reaction solution is dialyzed to remove unreacted monomers and excess oxidizing agent, and a polymer dispersion containing polyethylenedioxythiophene (PEDOT/PSS) doped with about 5% by mass of PSS is obtained. Obtained.
  • EDOT 3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • an accelerated test was performed by placing the electrolytic capacitor in a constant temperature bath with an atmosphere of 140°C and keeping the rated voltage applied for 1000 hours.
  • the ESR of the electrolytic capacitors was measured at 20° C. in the same manner as described above, and the average value of 20 electrolytic capacitors was obtained.
  • the ratio of the average value of ESR after the accelerated test to the average value of ESR in the initial stage was obtained and used as an index of ESR fluctuation in long-term use.
  • a rated voltage was applied to the electrolytic capacitor after the accelerated test in an environment of 20°C, and the leakage current value was measured 120 seconds later.
  • Tables 1-3 The evaluation results are shown in Tables 1-3.
  • A1 to A22 are examples, and B1 to B13 are comparative examples.
  • the result of each example was expressed as a relative value when the result of B1 was set to 100.
  • the lower numerical value of each anion or cation in Tables 1 to 3 is the concentration in the liquid component.
  • the numerical value in parentheses next to the second anion is the pKa of the second anion.
  • the electrolytic capacitor of the present disclosure can be used as a hybrid electrolytic capacitor. Electrolytic capacitors are particularly suitable for applications that require high reliability. However, the uses of electrolytic capacitors are not limited to these.
  • Capacitor element 11 Bottomed case 12: Sealing member 13: Seat plate 14A, 14B: Lead wire 15A, 15B: Lead tab 21: Anode body 22: Cathode body 23: Separator 24: Winding tape

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2022/028246 2021-07-26 2022-07-20 電解コンデンサ Ceased WO2023008288A1 (ja)

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US18/580,619 US12444549B2 (en) 2021-07-26 2022-07-20 Electrolytic capacitor

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WO2025047373A1 (ja) * 2023-08-31 2025-03-06 パナソニックＩｐマネジメント株式会社 電解コンデンサおよび電解コンデンサ用液状成分

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US12444549B2 (en) 2025-10-14

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