WO2017017947A1 - 電解コンデンサ - Google Patents

電解コンデンサ Download PDF

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Publication number
WO2017017947A1
WO2017017947A1 PCT/JP2016/003443 JP2016003443W WO2017017947A1 WO 2017017947 A1 WO2017017947 A1 WO 2017017947A1 JP 2016003443 W JP2016003443 W JP 2016003443W WO 2017017947 A1 WO2017017947 A1 WO 2017017947A1
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Prior art keywords
electrolytic capacitor
mass
capacitor according
dielectric layer
electrolytic
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English (en)
French (fr)
Japanese (ja)
Inventor
椿　雄一郎
青山　達治
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Priority to CN201680043408.4A priority Critical patent/CN107851519B/zh
Priority to JP2017531015A priority patent/JP6883735B2/ja
Publication of WO2017017947A1 publication Critical patent/WO2017017947A1/ja
Priority to US15/872,948 priority patent/US10373763B2/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
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • H01G9/008—Terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/07—Dielectric layers
    • 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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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 invention relates to an electrolytic capacitor having a solid electrolyte layer and an electrolytic solution.
  • Electrolytic capacitors As a small capacitor having a large capacity and a low ESR (equivalent series resistance), an anode body having a dielectric layer formed thereon, a solid electrolyte layer formed so as to cover at least a part of the dielectric layer, and an electrolytic solution Electrolytic capacitors are promising.
  • a ⁇ -conjugated conductive polymer is used for the solid electrolyte layer.
  • a solvent containing ethylene glycol and ⁇ -butyrolactone as the electrolytic solution from the viewpoint of enhancing the withstand voltage characteristics of the electrolytic capacitor.
  • adding an antioxidant to electrolyte solution etc. is also proposed (patent document 2).
  • Electrolytic capacitors are required to have low ESR, heat resistance, etc. in addition to withstand voltage characteristics. From the viewpoint of improving the heat resistance as well as the withstand voltage, it is considered desirable to include an acid in the solute of the electrolytic solution and to use a glycol compound as a solvent for the electrolytic solution. However, when a glycol compound is used as a solvent, when a long-term load test is performed at 100 ° C. or higher, low ESR is exhibited initially, but ESR tends to increase rapidly after a certain period of time.
  • an object of the present invention is to provide an electrolytic capacitor that has excellent withstand voltage characteristics and heat resistance and can maintain low ESR.
  • One aspect of the present invention includes an anode body having a dielectric layer, a solid electrolyte layer in contact with the dielectric layer of the anode body, and an electrolyte solution, and the electrolyte solution includes a solvent and a solute,
  • the solvent includes a glycol compound
  • the solute includes a carboxylic acid component and a base component
  • the solute includes 200 parts by mass or more of the carboxylic acid component with respect to 100 parts by mass of the base component.
  • an electrolytic capacitor that has excellent withstand voltage characteristics and heat resistance and can maintain a low ESR.
  • the electrolytic capacitor according to the present invention includes an anode body having a dielectric layer, a solid electrolyte layer in contact with the dielectric layer, and an electrolytic solution.
  • the electrolytic solution includes a solvent and a solute, the solvent includes a glycol compound, and the solute includes a carboxylic acid component and a base component.
  • the solute contains 200 parts by mass or more of the carboxylic acid component with respect to 100 parts by mass of the base component.
  • the solvent containing the glycol compound enhances the orientation or crystallinity of the conductive polymer contained in the solid electrolyte layer.
  • the electroconductivity of a solid electrolyte layer improves and ESR of an electrolytic capacitor becomes low.
  • the contact property between the solid electrolyte layer and the dielectric layer is improved, and the withstand voltage characteristic is also improved.
  • the conductive polymer is swollen by the glycol compound. Since the conductive polymer in the swollen state easily undergoes rearrangement, it is considered that the orientation or crystallinity is improved.
  • the electrolytic solution is easily held between the dielectric layer and the solid electrolyte layer, and appropriate insulation is easily maintained by the held electrolytic solution.
  • the ESR of the electrolytic capacitor can be kept low in the long term as well as in the initial period. It is considered that the deterioration of the conductivity of the solid electrolyte layer is suppressed by excessively containing the carboxylic acid component in the electrolytic solution. Note that the deterioration of the solid electrolyte layer is considered to be one of the causes due to the dedoping of the dopant from the conductive polymer.
  • the amount of the carboxylic acid component may be 200 parts by mass or more with respect to 100 parts by mass of the base component, preferably 400 parts by mass or more, more preferably 600 parts by mass or more, and 900 parts by mass. More preferably, the above is true. Thereby, the effect which suppresses the electroconductive deterioration of a solid electrolyte layer becomes large gradually. However, since the dissociation becomes difficult when there are too many carboxylic acid components, the amount of the carboxylic acid component is preferably 4500 parts by mass or less with respect to 100 parts by mass of the base component.
  • the pH of the electrolytic solution is preferably 4 or less, more preferably 3.8 or less, and still more preferably 3.6 or less.
  • the pH of the electrolytic solution is preferably 4 or less, more preferably 3.8 or less, and still more preferably 3.6 or less.
  • the ratio of the glycol compound contained in the solvent is desirably 50% by mass or more, more desirably 60% by mass or more, and further desirably 70% by mass or more.
  • the solvent can contain, in addition to the glycol compound, for example, a sulfone compound, a lactone compound, a carbonate compound, a monovalent or trivalent or higher alcohol, and the like.
  • a sulfone compound for example, sulfolane, dimethyl sulfoxide, diethyl sulfoxide and the like can be used.
  • lactone compound ⁇ -butyrolactone, ⁇ -valerolactone, and the like can be used.
  • the carbonate compound dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC) and the like can be used.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • EC ethylene carbonate
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • the glycol compound contains at least ethylene glycol.
  • ethylene glycol is the main component of the glycol compound. Since ethylene glycol has a low viscosity among glycol compounds, it easily dissolves excess carboxylic acid components. In addition, ethylene glycol has high thermal conductivity and excellent heat dissipation when a ripple current is generated, and thus has a large effect of improving heat resistance.
  • the proportion of ethylene glycol in the glycol compound is preferably 30% by mass or more, more preferably 50% by mass or more, and the glycol compound may be 100% by mass of ethylene glycol.
  • the glycol compound may contain, for example, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol having an average molecular weight of about 190 to 400, and the like.
  • 3 to 25% by mass of the solvent may be polyethylene glycol having an average molecular weight of 200 to 300.
  • a part of the carboxylic acid component may be derived from a salt with a base component. That is, a salt of a carboxylic acid component and a base component may be used as part of the solute. By using such a salt, the effect of improving the dissociation degree of the carboxylic acid component can be obtained. For example, 10% by mass to 50% by mass of the carboxylic acid component is desirably derived from a salt with the base component.
  • the base component is preferably at least one selected from the group consisting of primary amines, secondary amines and tertiary amines.
  • an amine component particularly a primary to tertiary amine, the effect of stabilizing ESR in the long term can be enhanced.
  • a quaternary amine may be used, but from the viewpoint of suppressing side reactions as much as possible, primary to tertiary amines exhibiting moderate basicity are desirable.
  • an aliphatic amine, an aromatic amine, a heterocyclic amine, or the like can be used, but an aliphatic amine having a molecular weight of 72 to 102 is preferable in terms of a high degree of dissociation.
  • Examples of primary to tertiary amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, N, N-diisopropylethylamine, tetramethylethylenediamine, hexamethylenediamine, spermidine, spermine, amantadine, aniline, Examples include phenethylamine, toluidine, pyrrolidine, piperidine, piperazine, morpholine, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, 4-dimethylaminopyridine and the like. These may be used alone or in combination of two or more. Of these, tertiary amines such as triethylamine and monoethyldimethylamine are particularly preferred.
  • the solute may further contain an aromatic compound (first aromatic compound) containing two or more hydroxyl groups.
  • the hydroxyl group of the first aromatic compound has an effect of stabilizing the conductive polymer by supplementing the action of the carboxylic acid component. Such a stabilizing action is considered to be related to the weakly acidic hydroxyl group of the first aromatic compound.
  • the hydroxyl group of the first aromatic compound is stable and hardly causes a side reaction such as an esterification reaction to proceed. Therefore, the first aromatic compound exhibits an effect of stabilizing the conductive polymer over a long period of time.
  • the aromatic ring of the first aromatic compound is preferably a C6 benzene ring or a C10 naphthalene ring from the viewpoint of suppressing an increase in the viscosity of the electrolytic solution.
  • the first aromatic compound desirably has two or more phenolic hydroxyl groups that are directly bonded to the aromatic ring in terms of long-term stability. Of these, divalent to tetravalent phenolic compounds are preferred. More specifically, it is more preferable to use at least one selected from the group consisting of catechol and pyrogallol as the first aromatic compound. Pyrogallol is particularly preferable in that it exhibits moderate acidity, and 90% by mass or more of the first aromatic compound is preferably pyrogallol.
  • the carboxylic acid component preferably contains an aromatic compound (second aromatic compound) having two or more carboxyl groups.
  • the carboxyl group of the second aromatic compound is stable and does not easily cause side reactions. Therefore, the first aromatic compound exhibits an effect of stabilizing the conductive polymer over a long period of time.
  • the second aromatic compound since the second aromatic compound exhibits moderate acidity in the electrolytic solution, the possibility of damaging the anode body due to corrosion is low.
  • the aromatic ring of the second aromatic compound is preferably a C6 benzene ring or a C10 naphthalene ring from the viewpoint of suppressing an increase in the viscosity of the electrolytic solution.
  • the second aromatic compound is preferably a divalent to tetravalent carboxylic acid in that it exhibits moderate acidity, and has a carboxyl group that directly binds to the ortho position of the aromatic ring in that the carboxyl group is easily stabilized. It is further desirable to have at least two. More specifically, as the second aromatic compound, it is more preferable to use at least one selected from the group consisting of o-phthalic acid and pyromellitic acid.
  • O-phthalic acid is particularly preferable in that the carboxyl group is easily stabilized and the effect of stabilizing the conductive polymer over a longer period of time is obtained, and 90% by mass or more of the second aromatic compound is o-phthalic acid. It is desirable that
  • the proportion of the solute contained in the electrolytic solution is preferably 2 to 30% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 30% by mass.
  • an excess carboxylic acid component can be included while appropriately including a base component effective for dissociation of the carboxylic acid component.
  • the increase in the viscosity of the electrolytic solution is small, and the voltage is hardly lowered.
  • the total amount of the carboxylic acid component (or the second aromatic compound), the base component, and the first aromatic compound is preferably 2 to 30% by mass of the electrolytic solution, and is 10 to 30% by mass. More desirably, it is more desirably 15 to 30% by mass.
  • the ratio of the first aromatic compound containing two or more hydroxyl groups is 0.3 to 70% by mass of the entire solute from the viewpoint of further improving the heat resistance of the electrolytic capacitor and further suppressing the deterioration of the solid electrolyte layer. Desirable is 3 to 40% by mass, more desirably 3 to 25% by mass.
  • the ratio of the second aromatic compound having two or more carboxyl groups is preferably 3 to 99% by mass, and 50 to 95% by mass of the entire solute from the viewpoint of further suppressing deterioration of the solid electrolyte layer. Is more desirably 70 to 95% by mass.
  • the solid electrolyte layer may be formed by a method in which a solution containing a monomer, a dopant, an oxidant, and the like is applied to the dielectric layer, and chemical polymerization or electrolytic polymerization is performed in situ.
  • a conductive polymer is applied to the dielectric layer from the viewpoint that excellent withstand voltage characteristics can be expected. That is, the solid electrolyte layer is formed by impregnating a dielectric layer with a polymer dispersion containing a liquid component and a conductive polymer dispersed in the liquid component to form a film covering at least a part of the dielectric layer.
  • the film is preferably formed by volatilizing a liquid component from the film.
  • the electrolytic solution is particularly effective for suppressing deterioration of the conductive polymer contained in the polymer dispersion, and is also effective for improving the orientation.
  • the concentration of the conductive polymer contained in the polymer dispersion is preferably 0.5 to 10% by mass.
  • the average particle diameter D50 of the conductive polymer is preferably 0.01 to 0.5 ⁇ m, for example.
  • the average particle diameter D50 is a median diameter in a volume particle size distribution determined by a particle size distribution measuring apparatus using a dynamic light scattering method.
  • the polymer dispersion having such a concentration is suitable for forming a solid electrolyte layer having an appropriate thickness and is easily impregnated in the dielectric layer.
  • polypyrrole, polythiophene, polyaniline and the like are preferable. These may be used alone or in combination of two or more, or may be a copolymer of two or more monomers. When the solid electrolyte layer contains such a conductive polymer, further improvement in the withstand voltage characteristic can be expected.
  • polypyrrole, polythiophene, polyaniline and the like mean polymers having a basic skeleton of polypyrrole, polythiophene, polyaniline and the like, respectively. Accordingly, polypyrrole, polythiophene, polyaniline and the like can also include their respective derivatives.
  • polythiophene includes poly (3,4-ethylenedioxythiophene) (PEDOT) and the like.
  • the weight average molecular weight of the conductive polymer is not particularly limited, but is, for example, 1000 to 100,000.
  • a dopant may be added to the conductive polymer. That is, the solid electrolyte layer may contain a dopant, and it is desirable that the solid electrolyte layer contains a polymer dopant from the viewpoint of suppressing dedoping from the conductive polymer.
  • Polymeric dopants include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, polyacrylic And anions such as acids. These may be used alone or in combination of two or more. These may be a homopolymer or a copolymer of two or more monomers. Of these, polystyrene sulfonic acid (PSS) is preferable.
  • PSS polystyrene sulfonic acid
  • the weight average molecular weight of the dopant is not particularly limited, but it is preferably, for example, 1000 to 100,000, from the viewpoint of easily forming a homogeneous solid electrolyte layer.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to the present embodiment
  • FIG. 2 is a schematic view in which a part of a capacitor element according to the electrolytic capacitor is developed.
  • the electrolytic capacitor includes, for example, a capacitor element 10, a bottomed case 11 that houses the capacitor element 10, a sealing member 12 that closes the opening of the bottomed case 11, a seat plate 13 that covers the sealing member 12, and a sealing member.
  • Lead wires 14A and 14B led out from the member 12 and penetrating the seat plate 13, lead tabs 15A and 15B connecting the lead wires and the electrodes of the capacitor element 10, and an electrolyte (not shown) are provided.
  • the vicinity of the open end of the bottomed case 11 is drawn inward, and the open end is curled so as to caulk the sealing member 12.
  • the sealing member 12 is formed of an elastic material containing a rubber component.
  • rubber components include butyl rubber (IIR), nitrile rubber (NBR), ethylene propylene rubber, ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), isoprene rubber (IR), hyperon rubber, silicone rubber, fluorine rubber, etc. Can be used.
  • the sealing member 12 may include a filler such as carbon black or silica.
  • the electrolytic solution it is necessary to consider the volatilization of the electrolytic solution to the outside through the sealing member 12 that forms the seal portion.
  • the electrolytic solution according to the present embodiment includes a glycol compound, it does not easily pass through the seal portion even at high temperatures. Therefore, an electrolytic capacitor having excellent heat resistance can be obtained.
  • the capacitor element 10 is manufactured from a wound body as shown in FIG.
  • the wound body is a semi-finished product of the capacitor element 10 and means that a solid electrolyte layer is not formed between the anode body 21 and the cathode body 22 having a dielectric layer on the surface.
  • the wound body includes an anode body 21 connected to the lead tab 15A, a cathode body 22 connected to the lead tab 15B, and a separator 23.
  • FIG. 2 has shown the state by which one part was expand
  • the anode body 21 includes a metal foil roughened so that the surface has irregularities, and a dielectric layer is formed on the metal foil having irregularities.
  • a solid electrolyte layer is formed by attaching a conductive polymer to at least a part of the surface of the dielectric layer.
  • the solid electrolyte layer may cover at least a part of the surface of the cathode body 22 and / or the surface of the separator 23.
  • the capacitor element 10 on which the solid electrolyte layer is formed is accommodated in the outer case together with the electrolytic solution.
  • Step of preparing anode body 21 having a dielectric layer First, a metal foil that is a raw material of anode body 21 is prepared.
  • the type of the metal is not particularly limited, but it is preferable to use a valve action metal such as aluminum, tantalum, or niobium or an alloy containing the valve action metal because the dielectric layer can be easily formed.
  • the surface of the metal foil is roughened.
  • a plurality of irregularities are formed on the surface of the metal foil.
  • the roughening is preferably performed by etching the metal foil.
  • the etching process may be performed by, for example, a direct current electrolytic method or an alternating current electrolytic method.
  • the metal foil can be formed by chemical conversion treatment.
  • the metal foil is immersed in a chemical conversion solution such as an ammonium adipate solution and heat treated.
  • a metal foil may be immersed in a chemical conversion liquid, and a voltage may be applied.
  • the anode body 21 is prepared by cutting the foil after processing into a desired size.
  • a metal foil can be used for the cathode body 22.
  • the type of metal is not particularly limited, but it is preferable to use a valve action metal such as aluminum, tantalum, or niobium or an alloy containing the valve action metal. If necessary, the surface of the anode body 22 may be roughened.
  • a winding body is produced using the anode body 21 and the cathode body 22.
  • the anode body 21 and the cathode body 22 are wound through the separator 23.
  • the lead tabs 15A and 15B can be planted from the wound body as shown in FIG.
  • a nonwoven fabric mainly composed of synthetic cellulose, polyethylene terephthalate, vinylon, aramid fiber, or the like can be used as the material of the separator 23, for example.
  • the material of the lead tabs 15A and 15B is not particularly limited as long as it is a conductive material.
  • the material of the lead wires 14A and 14B connected to each of the lead tabs 15A and 15B is not particularly limited as long as it is a conductive material.
  • the winding tape 24 is disposed on the outer surface of the cathode body 22 located in the outermost layer among the wound anode body 21, cathode body 22 and separator 23, and the end of the cathode body 22 is fastened. Secure with tape 24.
  • the wound body 21 is prepared by cutting a large-sized metal foil, the wound body may be further subjected to chemical conversion treatment in order to provide a dielectric layer on the cut surface of the anode body 21. .
  • the polymer dispersion is impregnated into the dielectric layer, and a film covering at least a part of the dielectric layer is formed.
  • the polymer dispersion includes a liquid component and a conductive polymer dispersed in the liquid component.
  • the polymer dispersion may be a solution in which a conductive polymer is dissolved in a liquid component, or a dispersion in which conductive polymer particles are dispersed in a liquid component.
  • the liquid component is volatilized from the formed film by drying, thereby forming a dense solid electrolyte layer covering at least a part of the dielectric layer. Since the polymer dispersion is uniformly distributed in the liquid component, it is easy to form a uniform solid electrolyte layer. Thereby, the capacitor element 10 is obtained.
  • the polymer dispersion can be obtained by, for example, a method of dispersing a conductive polymer in a liquid component, a method of polymerizing a precursor monomer in a liquid component, and generating particles of a conductive polymer.
  • Preferred polymer dispersions include, for example, poly (3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrene sulfonic acid (PSS), that is, PEDOT / PSS.
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS polystyrene sulfonic acid
  • the antioxidant of a conductive polymer may be added, since PEDOT / PSS hardly oxidizes, it is not necessary to use an antioxidant.
  • the liquid component may be water, a mixture of water and a non-aqueous solvent, or a non-aqueous solvent.
  • the non-aqueous solvent is not particularly limited, and for example, a protic solvent or an aprotic solvent can be used.
  • the protic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol and propylene glycol, and ethers such as formaldehyde and 1,4-dioxane.
  • aprotic solvent examples include amides such as N-methylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, esters such as methyl acetate, and ketones such as methyl ethyl ketone.
  • a method for applying the polymer dispersion to the surface of the dielectric layer for example, a method of immersing a wound body in a polymer dispersion accommodated in a container is simple and preferable.
  • the immersion time is, for example, 1 second to 5 hours, preferably 1 minute to 30 minutes, depending on the size of the wound body.
  • the impregnation is preferably performed under reduced pressure, for example, in an atmosphere of 10 to 100 kPa, preferably 40 to 100 kPa.
  • ultrasonic vibration may be applied to the wound body or the polymer dispersion while being immersed in the polymer dispersion. Drying after lifting the wound body from the polymer dispersion is preferably performed at 50 to 300 ° C., for example, and more preferably at 100 to 200 ° C.
  • the step of applying the polymer dispersion to the surface of the dielectric layer and the step of drying the wound body may be repeated twice or more. By performing these steps a plurality of times, the coverage of the solid electrolyte layer with respect to the dielectric layer can be increased. At this time, a solid electrolyte layer may be formed not only on the surface of the dielectric layer but also on the surfaces of the cathode body 22 and the separator 23.
  • a solid electrolyte layer is formed between the anode body 21 and the cathode body 22, and the capacitor element 10 is manufactured. Note that the solid electrolyte layer formed on the surface of the dielectric layer functions as a practical cathode material.
  • (V) Step of impregnating capacitor element 10 with electrolytic solution the capacitor element 10 is impregnated with the electrolytic solution.
  • the method for impregnating the capacitor element 10 with the electrolytic solution is not particularly limited.
  • a method of immersing the capacitor element 10 in an electrolytic solution accommodated in a container is simple and preferable.
  • the immersion time depends on the size of the capacitor element 10, it is, for example, 1 second to 5 minutes.
  • the impregnation is preferably performed under reduced pressure, for example, in an atmosphere of 10 to 100 kPa, preferably 40 to 100 kPa.
  • the capacitor element 10 is sealed. Specifically, first, the capacitor element 10 is housed in the bottomed case 11 so that the lead wires 14 ⁇ / b> A and 14 ⁇ / b> B are positioned on the upper surface where the bottomed case 11 opens.
  • a metal such as aluminum, stainless steel, copper, iron, brass, or an alloy thereof can be used.
  • the sealing member 12 formed so that the lead wires 14 ⁇ / b> A and 14 ⁇ / b> B penetrate is disposed above the capacitor element 10, and the capacitor element 10 is sealed in the bottomed case 11.
  • lateral drawing is performed in the vicinity of the open end of the bottomed case 11, and the open end is crimped to the sealing member 12 for curling.
  • the electrolytic capacitor as shown in FIG. 1 is completed by arrange
  • the wound type electrolytic capacitor has been described.
  • the scope of the present invention is not limited to the above, and other electrolytic capacitors, for example, a chip type electrolytic capacitor using a metal sintered body as an anode body.
  • the present invention can also be applied to a capacitor or a multilayer electrolytic capacitor using a metal plate as an anode body.
  • Example 1 In this example, a wound type electrolytic capacitor ( ⁇ 10.0 mm ⁇ L (length) 10.0 mm) having a rated voltage of 80 V and a rated capacitance of 38 ⁇ F was produced. Below, the specific manufacturing method of an electrolytic capacitor is demonstrated.
  • Etching was performed on an aluminum foil having a thickness of 100 ⁇ m to roughen the surface of the aluminum foil. Thereafter, a dielectric layer was formed on the surface of the aluminum foil by chemical conversion treatment. The chemical conversion treatment was performed by immersing an aluminum foil in an ammonium adipate solution and applying a voltage of 150 V thereto. Thereafter, the aluminum foil was cut so that the length ⁇ width was 6 mm ⁇ 120 mm to prepare an anode body.
  • the aluminum foil having a thickness of 50 ⁇ m was etched to roughen the surface of the aluminum foil. Thereafter, the aluminum foil was cut so that the length ⁇ width was 6 mm ⁇ 120 mm to prepare a cathode 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 winding the lead tab.
  • An anode lead wire and a cathode lead wire were respectively connected to the end portions of the lead tabs protruding from the wound body.
  • the formed wound body was subjected to a chemical conversion treatment again, and a dielectric layer was formed on the cut end portion of the anode body.
  • the end of the outer surface of the wound body was fixed with a winding tape to produce a wound body.
  • An electrolytic solution having the composition shown in Table A below containing ethylene glycol (EG) as a glycol compound and polyethylene glycol (PEG) having an average molecular weight of about 300 was prepared, and a capacitor element was added to the electrolytic solution in a reduced pressure atmosphere (40 kPa). Immerse for a minute. A part of the carboxylic acid component and the base component (triethylamine) were added as phthalic acid triethylamine (salt).
  • Capacitor element sealing The capacitor element impregnated with the electrolytic solution was sealed to complete the electrolytic capacitor. Specifically, the capacitor element is accommodated in the bottomed case so that the lead wire is positioned on the opening side of the bottomed case, and the sealing member formed so that the lead wire penetrates (elasticity including butyl rubber as a rubber component) The material was placed above the capacitor element, and the capacitor element was sealed in the bottomed case. Then, the electrolytic capacitor (A1) as shown in FIG. 1 was completed by drawing the vicinity of the open end of the bottomed case, further curling the open end, and arranging a seat plate on the curled portion. Thereafter, an aging treatment was performed at 130 ° C. for 2 hours while applying a rated voltage.
  • Example 2 An electrolytic capacitor A2 was prepared in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table B below was used, and evaluated in the same manner.
  • Example 3 An electrolytic capacitor A3 was produced in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table C below was used, and was evaluated in the same manner.
  • Comparative Example 1 An electrolytic capacitor B1 was prepared in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table D below was used, and was evaluated in the same manner.
  • the obtained electrolytic capacitor was measured for capacitance, ESR, and breakdown voltage (BDV). With respect to the breakdown voltage (BDV), a voltage was applied while boosting at a rate of 1.0 V / second, and the voltage when an overcurrent of 0.5 A flows was measured.
  • Example 4 An electrolytic capacitor A4 was prepared in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table E below was used, and was evaluated in the same manner.
  • Example 5 An electrolytic capacitor A5 was produced in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table F below was used, and was evaluated in the same manner.
  • Example 6 An electrolytic capacitor A6 was produced in the same manner as in Example 1 except that an electrolytic solution having the composition shown in Table G below was used, and was evaluated in the same manner. In addition, a part of carboxylic acid component (pyromellitic acid) and a base component (triethylamine) were added as pyromellitic acid ditriethylamine (salt).
  • carboxylic acid component pyromellitic acid
  • a base component triethylamine
  • Example 7 An electrolytic capacitor A7 was prepared in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table H below was used, and was evaluated in the same manner.
  • Example 8 An electrolytic capacitor A8 was produced in the same manner as in Example 1 except that the electrolytic solution having the composition shown in Table I below was used, and was evaluated in the same manner.
  • Example 9 An electrolytic capacitor A9 was produced in the same manner as in Example 1 except that an electrolytic solution having the composition shown in Table J below was used, and was similarly evaluated.
  • the present invention can be used for an electrolytic capacitor including a solid electrolyte layer covering at least a part of a dielectric layer and an electrolytic solution.

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JP2017069537A (ja) * 2015-09-30 2017-04-06 カーリットホールディングス株式会社 電解コンデンサ
CN108806988A (zh) * 2017-05-05 2018-11-13 常州华威电子有限公司 车载用耐高温电解电容器及其制备方法
WO2022025189A1 (ja) * 2020-07-31 2022-02-03 パナソニックＩｐマネジメント株式会社 電解コンデンサ
US11456120B2 (en) * 2018-12-28 2022-09-27 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor comprising an anode body, a cathode body and a conductive polymer and a liquid component disposed between the anode body and the cathode body
US12456587B2 (en) 2021-06-01 2025-10-28 Rubycon Corporation Solid electrolytic capacitor including electrolytic solution containing acid and amine, and method for manufacturing same

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CN113410058B (zh) * 2020-03-16 2024-07-19 钰邦科技股份有限公司 电容器单元及其制造方法
JP2023137006A (ja) * 2022-03-17 2023-09-29 日本ケミコン株式会社 電解コンデンサ
JP7452742B2 (ja) 2022-07-01 2024-03-19 東ソー株式会社 焼結体の製造方法

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CN108806988A (zh) * 2017-05-05 2018-11-13 常州华威电子有限公司 车载用耐高温电解电容器及其制备方法
CN108806988B (zh) * 2017-05-05 2024-02-13 常州华威电子有限公司 车载用耐高温电解电容器及其制备方法
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WO2022025189A1 (ja) * 2020-07-31 2022-02-03 パナソニックＩｐマネジメント株式会社 電解コンデンサ
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US12456587B2 (en) 2021-06-01 2025-10-28 Rubycon Corporation Solid electrolytic capacitor including electrolytic solution containing acid and amine, and method for manufacturing same

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