WO2021153750A1 - 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
WO2021153750A1
WO2021153750A1 PCT/JP2021/003298 JP2021003298W WO2021153750A1 WO 2021153750 A1 WO2021153750 A1 WO 2021153750A1 JP 2021003298 W JP2021003298 W JP 2021003298W WO 2021153750 A1 WO2021153750 A1 WO 2021153750A1
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Prior art keywords
compound
capacitor
layer
conductive polymer
capacitor element
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English (en)
French (fr)
Japanese (ja)
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義和 平田
慶明 石丸
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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 CN202180011088.5A priority Critical patent/CN115023780B/zh
Priority to JP2021574699A priority patent/JP7724421B2/ja
Publication of WO2021153750A1 publication Critical patent/WO2021153750A1/ja
Priority to US17/813,391 priority patent/US12417883B2/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
    • H01G9/0029—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
    • H01G9/012—Terminals specially adapted for solid 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
    • H01G9/004—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
    • H01G9/15—Solid electrolytic capacitors
    • H01G9/151—Solid electrolytic capacitors with wound foil electrodes
    • 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

Definitions

  • This disclosure relates to electrolytic capacitors and their manufacturing methods.
  • Capacitors used in electronic devices are required to have a large capacity and a small equivalent series resistance (ESR) value in the high frequency region.
  • ESR equivalent series resistance
  • an electrolytic capacitor using a conductive polymer such as polypyrrole, polythiophene, polyfuran, or polyaniline is promising.
  • Patent Document 1 discloses a method of impregnating a capacitor element formed by winding an anode foil and a cathode foil with a separator to impregnate a dispersion containing a conductive polymer and a solvent.
  • one of the purposes of the present disclosure is to provide an electrolytic capacitor having high characteristics and a method for manufacturing the electrolytic capacitor.
  • the production method comprises a step (i) of forming a capacitor element precursor including a separator and a foil-shaped anode and a foil-shaped cathode body facing each other across the separator, and from sugar and polyhydric alcohol.
  • the first compound which is at least one compound selected from the above group and has a melting point of 50 ° C. or higher, is placed inside the capacitor element precursor, and the capacitor that has undergone the step (ii).
  • the step (iii) of forming a first layer containing the first conductive polymer inside the element precursor is included.
  • the step (iii) includes a step (iii-a) of impregnating the capacitor element precursor that has undergone the step (ii) with a first aqueous dispersion containing the first conductive polymer, and impregnation. This includes a step (iii-b) of forming the first layer by drying the first aqueous dispersion.
  • the electrolytic capacitor is an electrolytic capacitor including a capacitor element, and the capacitor element includes a separator, a foil-shaped anode body and a foil-shaped cathode body facing each other so as to sandwich the separator, and the anode body.
  • a first compound comprising the cathode body and an electrolyte layer in contact with the separator, wherein the electrolyte layer is at least one compound selected from the group consisting of sugars and polyhydric alcohols and has a melting point of 50 ° C. or higher.
  • the electrolyte layer contains the compound 1 and the first conductive polymer, and the electrolyte layer has an unevenly distributed portion in which the first compound is unevenly distributed.
  • an electrolytic capacitor having high characteristics can be obtained.
  • FIG. 1 It is sectional drawing which shows typically an example of the electrolytic capacitor of this disclosure. It is a figure which shows a part of the electrolytic capacitor shown in FIG. 1 schematically. It is sectional drawing which shows typically a part of the example of the capacitor element included in the electrolytic capacitor of this disclosure. It is sectional drawing which shows typically a part of another example of the capacitor element included in the electrolytic capacitor of this disclosure.
  • the melting point is a value at 1 atm unless otherwise specified.
  • the viscosity is a value at room temperature (25 ° C.) at 1 atm unless otherwise specified.
  • an electrolytic capacitor having high characteristics can be obtained by filling the capacitor element precursor with a conductive polymer by a specific method. This disclosure is based on this new finding.
  • the electrolytic capacitor of the present disclosure is an electrolytic capacitor including a capacitor element.
  • the capacitor element includes a separator, a foil-shaped anode and a foil-shaped cathode body facing each other so as to sandwich the separator, and an anode, a cathode body, and an electrolyte layer in contact with the separator.
  • the electrolyte layer contains at least one compound selected from the group consisting of sugars and polyhydric alcohols, the first compound having a melting point of 50 ° C. or higher, and the first conductive polymer.
  • the electrolyte layer has an unevenly distributed portion in which the first compound is unevenly distributed.
  • the electrolytic capacitor of the present disclosure may be the first electrolytic capacitor described below, or may be the second electrolytic capacitor described below.
  • the first electrolytic capacitor and the second electrolytic capacitor have different electrolyte layers.
  • examples of embodiments include embodiments that belong to both the first electrolytic capacitor and the second electrolytic capacitor.
  • the first compound is unevenly distributed in at least a part of at least one selected from the group consisting of a portion in contact with the anode body, a portion in contact with the cathode body, and a portion in contact with the separator. It has an uneven distribution part.
  • the unevenly distributed portion where the first compound is unevenly distributed may be at least a part of the portion in contact with the anode body, at least a part of the portion in contact with the cathode body, or the portion in contact with the separator. It may be at least part of it, or it may be at least part of two or more of them (eg, all parts).
  • the electrolyte layer of the second electrolytic capacitor is formed on at least a second layer formed on at least a part of the surface of the anode body and the cathode body and containing the second conductive polymer, and at least on the second layer. It also includes a first layer containing a first conductive polymer.
  • the electrolyte layer of the second electrolytic capacitor has an unevenly distributed portion in which the first compound is unevenly distributed at least in a part of a portion in contact with the interface between the first layer and the second layer.
  • the first compound present in the uneven distribution portion improves the adhesiveness of the first conductive polymer due to its hydroxyl group. As a result, good characteristics (particularly low ESR) can be achieved. Further, since the stability of the electrolyte layer is improved by improving the adhesiveness of the first conductive polymer, it is possible to improve the reliability of the electrolytic capacitor. Further, by unevenly distributing the first compound, it is possible to form a thick conductive polymer layer in the portion.
  • the electrolyte layer of the first electrolytic capacitor may be composed of the first compound and the first conductive polymer, or may be composed of them and other substances.
  • the electrolyte layer of the second electrolytic capacitor may be composed of the first compound and the first and second conductive polymers, or may be composed of them and other substances.
  • the electrolyte layer of the electrolytic capacitor of the present disclosure may be an electrolyte layer (hybrid type electrolyte layer) containing a conductive polymer and a liquid component (non-aqueous solvent or non-aqueous electrolyte solution) described later. good.
  • the first and second conductive polymers (and the dopant added thereto) and the liquid component those used for the known electrolyte layer of the electrolytic capacitor may be used.
  • the electrolyte layer of the electrolytic capacitor of the present disclosure is a layer in which the above-mentioned conductive polymer is a main component (for example, the content is 50% by mass or more).
  • the electrolyte layer contains a liquid component, the liquid component is not considered in the calculation of the content of the conductive polymer in the electrolyte layer.
  • the first compound contained in the electrolyte layer of the electrolytic capacitor of the present disclosure will be described below.
  • the first compound is at least one compound selected from the group consisting of sugars and polyhydric alcohols, and has a melting point of 50 ° C. or higher.
  • the melting point of the first compound is preferably higher than the temperature at which the capacitor is used.
  • the melting point of the first compound may be in the range of 80 ° C. to 300 ° C. (for example, the range of 120 ° C. to 300 ° C.).
  • sugar examples include glucose and the like.
  • polyhydric alcohols examples include mannitol, sorbitol, xylitol, pentaerythritol, and trimethylolpropane.
  • mannitol, sorbitol, xylitol, pentaerythritol and the like may be called sugar alcohols.
  • the first compound may be a sugar alcohol.
  • the number of hydroxyl groups contained in the first compound may be in the range of 2 to 12 (for example, the range of 2 to 4).
  • the first compound is a water-soluble compound.
  • an organic compound containing a plurality of hydroxyl groups (-OH) bonded to a carbon atom for example, an organic compound that is not a polymer
  • a melting point in the above range is used. You may use it.
  • the molecular weight of the organic compound and the number of hydroxyl groups contained in the organic compound may each be within the above ranges exemplified for the first compound.
  • the first compound may be at least one selected from the group consisting of glucose, mannitol, sorbitol, xylitol, pentaerythritol, and trimethylolpropane.
  • Glucose has a melting point of about 146 to 150 ° C
  • mannitol has a melting point of about 165 to 169 ° C
  • sorbitol has a melting point of about 93 to 95 ° C
  • xylitol has a melting point of about 92 to 97 ° C
  • pentaerythritol has a melting point of about 257 to 260 ° C.
  • Trimethylol propane has a melting point of about 56 to 58 ° C.
  • the melting points of these substances may vary depending on the structure (stereoisomer). Glucose, mannitol, and pentaerythritol are preferred because of their high melting point.
  • the first conductive polymer (conductive polymer) used in the electrolytic capacitor of the present disclosure will be described below.
  • the first conductive polymer include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, and derivatives thereof.
  • the derivatives include polymers based on polypyrrole, polythiophene, polyfuran, polyaniline, and polyacetylene.
  • derivatives of polythiophene include poly (3,4-ethylenedioxythiophene) and the like.
  • These conductive polymers may be used alone or in combination of two or more.
  • the first conductive polymer may be a copolymer of two or more kinds of monomers.
  • the weight average molecular weight of the first conductive polymer is not particularly limited, and may be in the range of, for example, 1000 to 100,000.
  • a preferred example of the first conductive polymer is poly (3,4-ethylenedioxythiophene) (PEDOT).
  • Dopants may be added to the first conductive polymer. From the viewpoint of suppressing dedoping from the first conductive polymer, it is preferable to use a polymer dopant.
  • high molecular weight dopants 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, Includes polyacrylic acid and the like. These may be used alone or in combination of two or more. These may be added in the form of salts.
  • the polymeric dopant may be present in the electrolyte in the form of an anion in which a cation (eg, a proton) is dissociated from at least a portion of the acidic group.
  • a cation eg, a proton
  • a preferred example of a dopant is polystyrene sulfonic acid (PSS).
  • the weight average molecular weight of the dopant is not particularly limited. From the viewpoint of facilitating the formation of a homogeneous electrolyte layer, the weight average molecular weight of the dopant may be in the range of 1000 to 100,000.
  • the first conductive polymer may be a polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene).
  • the polymer exemplified for the first conductive polymer may be used as the second conductive polymer constituting the second layer of the second electrolytic capacitor.
  • the first conductive polymer and the second conductive polymer may be the same or different.
  • the second layer of the electrolyte layer of the second electrolytic capacitor may contain at least one compound selected from the group consisting of sugars and polyhydric alcohols and having a melting point of 50 ° C. or higher. ..
  • the compound exemplified for the first compound may be used.
  • the first compound and the second compound may be the same or different.
  • the second layer contains the second compound
  • the second layer is at least one portion selected from the group consisting of a portion in contact with the anode body, a portion in contact with the cathode body, and a portion in contact with the separator. At least a part thereof may have an uneven distribution portion in which the second compound is unevenly distributed.
  • the electrolyte layer of the electrolytic capacitor of the present disclosure may contain a non-aqueous solvent or a non-aqueous electrolyte solution.
  • the non-aqueous solvent and the non-aqueous electrolytic solution contained in the electrolyte layer may be collectively referred to as “liquid component (L)”.
  • the liquid component (L) may be a substance that is liquid at room temperature (25 ° C.) or may be a substance that is liquid at the temperature at which the electrolytic capacitor is used.
  • a preferred example of the liquid component (L) is a liquid in which the first compound is substantially insoluble.
  • the non-aqueous solvent may be an organic solvent or an ionic liquid.
  • non-aqueous solvents include polyhydric alcohols such as ethylene glycol and propylene glycol, cyclic sulfones such as sulfolane (SL), lactones such as ⁇ -butyrolactone ( ⁇ BL), N-methylacetamide, N, N-. Includes amides such as dimethylformamide and N-methyl-2-pyrrolidone, esters such as methyl acetate, carbonate compounds such as propylene carbonate, ethers such as 1,4-dioxane, ketones such as methylethylketone, and formaldehyde. ..
  • a polymer solvent may be used as the non-aqueous solvent.
  • the polymer solvent include polyalkylene glycols, derivatives of polyalkylene glycols, compounds in which at least one hydroxyl group in a polyhydric alcohol is replaced with polyalkylene glycol (including a derivative), and the like.
  • examples of polymer-based solvents include polyethylene glycol (PEG), polyethylene glycol glyceryl ether, polyethylene glycol diglyceryl ether, polyethylene glycol sorbitol ether, polypropylene glycol, polypropylene glycol glyceryl ether, and polypropylene glycol diglyceryl ether.
  • Polyethylene glycol sorbitol ether, polybutylene glycol and the like are included.
  • the polymer solvent further include a copolymer of ethylene glycol-propylene glycol, a copolymer of ethylene glycol-butylene glycol, a copolymer of propylene glycol-butylene glycol, and the like.
  • the non-aqueous solvent one type may be used alone, or two or more types may be mixed and used.
  • the liquid component (L) may contain an acid component and a base component.
  • acid components include maleic acid, phthalic acid, benzoic acid, pyromellitic acid, resorcinic acid and the like.
  • basic components include 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonen-5,1,2-dimethylimidazolinium, 1, 2,4-trimethylimidazoline, 1-methyl-2-ethyl-imidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl-2-heptyl imidazoline, 1-methyl-2- (3'heptyl) imidazoline, 1-Methyl-2-dodecylimidazoline, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-methylimidazole, 1-methylbenzoimidazole and the like are included.
  • the non-aqueous electrolyte solution contains a non-aqueous solvent and a solute (for example, an organic salt) dissolved therein.
  • a solute for example, an organic salt
  • examples of the non-aqueous solvent constituting the non-aqueous electrolytic solution include the above-mentioned examples of the non-aqueous solvent.
  • solutes include inorganic salts and organic salts.
  • An organic salt is a salt in which at least one of an anion and a cation contains an organic substance.
  • organic salts include trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono1,2,3,4-tetramethylimidazolinium phthalate, mono 1,3-dimethyl-2-phthalate. Includes ethylimidazolinium and the like.
  • the pH of the liquid component (L) may be less than 7, or 5 or less.
  • the capacitor element of the electrolytic capacitor of the present disclosure may be a winding type or a laminated type.
  • the foil-shaped anode body, the foil-shaped cathode body, and the separator are wound so that the separator is arranged between the anode body and the cathode body.
  • the foil-shaped anode body, the foil-shaped cathode body, and the separator are folded in a zigzag shape so that the separator is arranged between the anode body and the cathode body.
  • the anode, cathode, and separator of the electrolytic capacitor of the present disclosure are not particularly limited, and known ones may be used. Specific examples of these will be described below.
  • the anode has a dielectric layer on its surface.
  • a metal foil having a dielectric layer formed on its surface can be used as the anode body.
  • the type of metal constituting the metal foil is not particularly limited. Examples of metals constituting the metal foil include valve-acting metals such as aluminum, tantalum, niobium, and titanium, and alloys of valve-acting metals because of the ease of formation of the dielectric layer. ..
  • a preferred example is aluminum and aluminum alloys.
  • the surface of the anode body is roughened, and the dielectric layer is formed on the roughened surface. The electrolyte layer is in contact with the dielectric layer of the anode.
  • a metal foil can be used for the cathode body.
  • the type of metal constituting the metal foil is not particularly limited.
  • the metals that make up the metal leaf include valvular metals such as aluminum, tantalum, niobium, titanium, and alloys of valvular metals.
  • a preferred example is aluminum and aluminum alloys.
  • the surface of the cathode body may be provided with a chemical conversion film, and a metal (dissimilar metal) or non-metal film different from the metal constituting the cathode body may be provided.
  • dissimilar metals and non-metals include metals such as titanium and non-metals such as carbon.
  • separator As the separator, a sheet-like material that can be impregnated with an electrolyte can be used. For example, a sheet-like material that has insulating properties and can be impregnated with an electrolyte may be used.
  • the separator may be a woven fabric, a non-woven fabric, or a porous membrane. Examples of separator materials include cellulose, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, vinylon, nylon, aromatic polyamide, polyimide, polyamideimide, polyetherimide, rayon, and glass.
  • the electrolyte of the electrolytic capacitor of the present disclosure contains the first compound.
  • this first compound it is possible to improve the strength of the separator. If a separator having low strength (for example, a separator made of cellulosic natural fiber) is used, characteristics such as withstand voltage may be deteriorated. By using the hydroxyl group-containing compound (C), such deterioration of characteristics can be suppressed. The effect of reinforcing the separator can be obtained regardless of the type of separator.
  • the electrolytic capacitor of the present disclosure can be manufactured. Since the matters described about the electrolytic capacitor of the present disclosure can be applied to the following manufacturing methods, duplicate description may be omitted. For example, since the components of the electrolytic capacitor of the present disclosure (anode body, cathode body, separator, and components of the electrolyte layer) have been described above, duplicate description may be omitted. Specifically, since the first and second compounds, the first and second conductive polymers, the separator, and the liquid component (L) have been described above, overlapping description may be omitted. In addition, the matters described below can be applied to the above-described electrolytic capacitors of the present disclosure.
  • This manufacturing method includes steps (i) to (iii).
  • Step (i) is a step of forming a capacitor element precursor including a separator and a foil-shaped anode body and a foil-shaped cathode body facing each other with the separator interposed therebetween.
  • the capacitor element precursor is an element before the electrolyte layer is formed.
  • the foil-shaped anode body may be formed by a known method. For example, first, a metal foil as a raw material for an anode body is prepared, and the surface of the metal foil is roughened. The roughening can be performed by, for example, etching by a DC electrolysis method or an AC electrolysis method. Next, a dielectric layer is formed on the surface of the roughened metal foil. The dielectric layer can be formed, for example, by chemical conversion treatment of a metal foil. The surface of the metal foil is oxidized by the chemical conversion treatment of the metal foil, whereby a dielectric layer which is an oxide film is formed. In this way, the anode body is formed.
  • lead terminals for making electrical connections are connected to the anode body and the cathode body.
  • the first electrolytic capacitor is a winding type capacitor
  • a foil-shaped anode body, a foil-shaped cathode body, and a separator can be wound together to form a capacitor element precursor. At this time, they are wound so that the separators are arranged between the anode body and the cathode body.
  • the capacitor element is a laminated capacitor
  • the foil-shaped anode body, the foil-shaped cathode body, and the separator can be bent together in a zigzag manner to form a capacitor element precursor. At this time, they are bent so that the separators are arranged between the anode body and the cathode body.
  • Step (ii) is a step of arranging the first compound, which is at least one compound selected from the group consisting of sugars and polyhydric alcohols and has a melting point of 50 ° C. or higher, inside the capacitor element precursor.
  • Step (ii) may be a step of precipitating the first compound inside the capacitor element precursor. Therefore, in the following description, “arrangement” may be read as “precipitation”.
  • the step (ii) may include a step (ii-a) and a step (ii-b).
  • the step (ii-a) is a step of impregnating the capacitor element precursor with the first aqueous treatment liquid containing the first compound.
  • the step (ii-a) can be performed, for example, by immersing the capacitor element precursor in the first aqueous treatment liquid.
  • the immersion time is not limited, and may be 1 minute or more and less than 20 minutes.
  • the entire capacitor element precursor may be immersed in the first aqueous treatment solution, or only a part of the capacitor element precursor may be immersed in the first aqueous treatment solution. For example, only a portion of 50% or less in the longitudinal direction (axial direction in the case of a wound body) of the capacitor element precursor may be immersed in the first aqueous treatment liquid.
  • the step (ii-a) may be performed at room temperature or at a temperature other than room temperature (for example, a temperature higher than room temperature). Further, the step (ii-a) may be performed under atmospheric pressure or in an environment other than atmospheric pressure (for example, under reduced pressure).
  • the first aqueous treatment liquid is a treatment liquid containing water.
  • the amount of water contained in the liquid (solvent) constituting the first aqueous treatment liquid is, for example, in the range of 50 to 100% by mass.
  • the first compound is dissolved in the first aqueous treatment solution. That is, the first aqueous treatment liquid may be a solution in which the first compound is dissolved. In a typical example, the first aqueous treatment solution is an aqueous solution of the first compound.
  • the content (concentration) of the first compound in the first aqueous treatment solution may be in the range of 3 to 50% by mass (for example, in the range of 5 to 15% by mass). ..
  • the first aqueous treatment liquid may contain components other than the first compound, if necessary.
  • the first aqueous treatment liquid does not have to contain a polymer.
  • the first aqueous treatment liquid does not have to contain the first conductive polymer. Since the first aqueous treatment liquid containing no polymer has a low viscosity, impregnation into the capacitor element precursor becomes easy.
  • the polymer means a polymer having a weight average molecular weight of 1000 or more.
  • Step (ii-b) is a step of arranging the first compound inside the capacitor element precursor by drying the impregnated first aqueous treatment liquid. Drying is usually done by heating. Step (ii-b) may be performed under atmospheric pressure or in an environment other than atmospheric pressure (for example, under reduced pressure).
  • the drying temperature in step (ii-b) may be a temperature equal to or higher than the melting point of the first compound, and further, the boiling point of the first aqueous treatment liquid under the pressure for drying in step (ii-b). The temperature may be higher than that (for example, 100 ° C. or higher).
  • the drying temperature in step (ii-b) is a temperature equal to or higher than the boiling point of the first aqueous treatment liquid under the pressure for drying step (ii-b) (for example, 100 ° C. or higher). , The temperature above and below the boiling point of the first compound under the pressure of drying step (ii-b). By drying at a temperature equal to or higher than the melting point of the first compound, the permeability of the first compound to the capacitor element precursor can be enhanced.
  • step (ii) may be repeated as necessary. By repeating step (ii), the amount of the first compound precipitated can be increased.
  • the condenser element precursor is impregnated with the melt of the first compound to carry out the step ( ii) may be performed.
  • the step (iii) is a step of forming a first layer containing the first conductive polymer inside the capacitor element precursor that has undergone the step (ii).
  • the first layer formed in the step (iii) may be referred to as a “first layer (CL1)”.
  • the first layer (CL1) is a layer that can serve as an electrolyte layer of the first electrolytic capacitor.
  • the first layer (CL1) is a layer that can be the first layer of the electrolyte layer of the second electrolytic capacitor.
  • Step (iii) includes step (iii-a) and step (iii-b).
  • the step (iii-a) is a step of impregnating the capacitor element precursor that has undergone the step (ii) with the first aqueous dispersion containing the first conductive polymer.
  • the step (iii-a) can be performed, for example, by immersing the capacitor element precursor in the first aqueous dispersion.
  • the immersion time is not limited, and may be 1 second or more and 30 minutes or less.
  • the entire capacitor element precursor may be immersed in the first aqueous dispersion, or only a part of the capacitor element precursor may be immersed in the first aqueous dispersion. For example, only a portion of 50% or less in the longitudinal direction (axial direction in the case of a wound body) of the capacitor element precursor may be immersed in the first aqueous dispersion.
  • the step (iii-a) may be performed at room temperature or at a temperature other than room temperature (for example, a temperature higher than room temperature). Further, the step (iii-a) may be performed under atmospheric pressure or in an environment other than atmospheric pressure (for example, under reduced pressure).
  • the first aqueous dispersion is a treatment liquid containing water.
  • the amount of water contained in the aqueous liquid (dispersion medium) constituting the first aqueous dispersion is, for example, in the range of 2 to 100% by mass.
  • the aqueous liquid may be water.
  • the first conductive polymer is dispersed in an aqueous liquid. That is, the first aqueous dispersion is a suspension in which the first conductive polymer is dispersed in the aqueous liquid.
  • the content (concentration) of the first conductive polymer in the first aqueous dispersion may be in the range of 0.1 to 20% by mass (for example, in the range of 0.5 to 3% by mass).
  • the viscosity of the first aqueous dispersion may be in the range of 1 mPa ⁇ s to 100 mPa ⁇ s, or even in the range of 1 mPa ⁇ s to 40 mPa ⁇ s (for example, the range of 1 mPa ⁇ s to 25 mPa ⁇ s). good.
  • the lower the viscosity of the first aqueous dispersion the easier it is to impregnate the capacitor element precursor.
  • the first aqueous dispersion preferably does not contain the above-mentioned first compound. By not adding the first compound, the viscosity of the first aqueous dispersion can be reduced. Even when the first aqueous dispersion contains the first compound, it is preferably contained within a range in which the viscosity of the first aqueous dispersion is a certain value or less (for example, 40 mPa ⁇ s or less or 25 mPa ⁇ s or less).
  • a dopant may be added to the first conductive polymer.
  • the first aqueous dispersion may contain components other than the first conductive polymer and dopant, if necessary.
  • Step (iii-b) is a step of forming the first layer (CL1) by drying the impregnated first aqueous dispersion.
  • the first layer (CL1) comes into contact with the separator.
  • the first layer (CL1) may also be in contact with the anode and / or cathode.
  • the first layer (CL1) contains a first conductive polymer as a major component.
  • the method for drying the first aqueous dispersion may be performed in at least one atmosphere selected from a drying atmosphere, a reduced pressure atmosphere, and a heating atmosphere, and usually at least heating is performed.
  • the heating temperature in step (iii-b) is a temperature equal to or higher than the boiling point of the first aqueous dispersion under the pressure for drying step (iii-b) (for example, 100 ° C. or higher). It is a temperature below the melting point of the first compound under the pressure of drying in step (iii-b).
  • the heating temperature in the step (iii-b) is a temperature equal to or higher than the boiling point of the first aqueous dispersion under the pressure for drying in the step (iii-b) (for example, 100 ° C. or higher) and the step (for example, 100 ° C. or higher).
  • the temperature may be higher than the melting point of the first compound and lower than the boiling point under the pressure for drying iii-b).
  • the treatment is carried out with the first aqueous treatment liquid containing the first compound, and then the first aqueous dispersion is impregnated. Therefore, the impregnation of the first aqueous dispersion is easy. Further, by arranging the first compound in the capacitor element precursor in advance, it becomes possible to firmly fix the first conductive polymer to be impregnated thereafter. As a result, an electrolytic capacitor having high characteristics can be manufactured.
  • the first electrolytic capacitor can be manufactured by the first manufacturing method (M1)
  • the second electrolytic capacitor can be manufactured by the second manufacturing method (M2).
  • the first compound is placed on at least a part of at least one surface (S1) selected from the group consisting of the surface of the anode body, the surface of the cathode body, and the surface of the separator.
  • the step (ii-a) in the step (ii-a), at least a part of at least one surface (S1) selected from the group consisting of the surface of the anode body, the surface of the cathode body, and the surface of the separator.
  • the capacitor element precursor may be impregnated with the first aqueous treatment liquid so as to come into contact with each other.
  • the first compound in step (ii-b), may be placed on at least a part of the at least one surface (S1) by drying the impregnated first aqueous treatment liquid.
  • the step (iii) is performed in a state where the first compound is precipitated on at least a part of the surface (S1), and the first layer (CL1) is formed.
  • the first layer (CL1) to be formed contains the first compound in at least a part of at least one part selected from the group consisting of a part in contact with the anode body, a part in contact with the cathode body, and a part in contact with the separator. It has unevenly distributed parts. Therefore, the first conductive polymer in the first layer (CL1) is fixed by the first compound.
  • the step (ii-a) can be carried out by treating with the first aqueous treatment liquid after assembling the capacitor element precursor and before impregnating with the polymer.
  • the second manufacturing method (M2) may further include step (X) between steps (i) and step (ii).
  • the step (X) includes a step (Xa) and a step (Xb).
  • the step (Xa) is a step of impregnating the capacitor element precursor with a second aqueous dispersion containing the second conductive polymer.
  • Step (X-b) is a second layer containing a second conductive polymer on at least a portion of the surface of the anode and cathode by drying the impregnated second aqueous dispersion. Is the process of forming.
  • This second layer may be referred to as "second layer (CL2)" below.
  • the second layer (CL2) is a conductive polymer layer.
  • Steps (X-a) and (X-b) are steps (iii-a) and (iii), respectively, except that a second conductive polymer is used instead of the first conductive polymer.
  • -B) can be performed in the same manner.
  • the second aqueous dispersion can be prepared in the same manner as the first aqueous dispersion, except that the second conductive polymer is used instead of the first conductive polymer.
  • the second conductive polymer may be the same as or different from the first conductive polymer.
  • the implementation conditions of the step (iii) and the implementation conditions of the step (X) may be the same or different.
  • the average particle size of the second conductive polymer may be smaller than the average particle size of the first conductive polymer.
  • the average particle size is a volume-based median diameter (D 50 ).
  • the median diameter (D 50 ) is determined using, for example, a laser diffraction / scattering particle size distribution measuring device.
  • the average particle size of the first conductive polymer may be in the range of 0.1 ⁇ m to 0.5 ⁇ m.
  • the average particle size of the second conductive polymer may be in the range of 0.01 ⁇ m to 0.2 ⁇ m. In these ranges, the average particle size of the second conductive polymer may be smaller than the average particle size of the first conductive polymer.
  • the first compound is placed on the second layer (CL2) in the step (ii).
  • the capacitor element precursor that has undergone the step (X) is impregnated with the first aqueous treatment liquid
  • the impregnated first solution is impregnated.
  • the first compound may be placed on the surface of the second layer (CL2) by drying the aqueous treatment solution.
  • the step (iii) is performed in a state where the first compound is precipitated on the surface of the second layer (CL2), and the first layer (CL1) is formed.
  • the electrolyte layer of the second electrolytic capacitor is an unevenly distributed portion in which the first compound is unevenly distributed in at least a part of a portion in contact with the interface between the first layer (CL1) and the second layer (CL2).
  • the conductive polymer can be firmly fixed at the interface between the first layer (CL1) and the second layer (CL2).
  • the second aqueous dispersion may contain at least one compound selected from the group consisting of sugars and polyhydric alcohols and having a melting point of 50 ° C. or higher.
  • the viscosity of the second aqueous dispersion becomes high, the impregnation property of the second aqueous dispersion is not high.
  • step (ii) and step (iii) after that the filling rate of the first conductive polymer can be increased. Therefore, an electrolytic capacitor having high characteristics can be obtained.
  • the production method (M2) is a second compound having a melting point of 50 ° C. or higher, which is at least one compound selected from the group consisting of sugars and polyhydric alcohols between the step (i) and the step (X). May further include the step (Y) of arranging the above in the capacitor element precursor.
  • Step (Y) The step (Y) includes a step (Ya) and a step (Yb).
  • Step (YA) brings the second compound into contact with at least a portion of at least one surface (S2) selected from the group consisting of the surface of the anode body, the surface of the cathode body, and the surface of the separator.
  • This is a step of impregnating the capacitor element precursor with the second aqueous treatment liquid contained therein.
  • the step (Yb) is a step of arranging the second compound on at least a part of at least one surface (S2) by drying the impregnated second aqueous treatment liquid.
  • Steps (YA) and (Yb) are similar to steps (ii-a) and (ii-b), respectively, except that a second compound is used in place of the first compound. It can be carried out.
  • the second aqueous treatment solution can be prepared in the same manner as the first aqueous treatment solution, except that the second compound is used instead of the first compound.
  • the second compound may be the same as or different from the first compound.
  • the implementation conditions of step (ii) and the implementation conditions of step (Y) may be the same or different.
  • the drying in the step (iii-b) may be performed at a temperature equal to or higher than the melting point of the first compound. According to this drying condition, the first compound arranged by the step (ii) can be melted, and the stickiness by the first compound can be further enhanced.
  • step (X-b) may be carried out at a temperature equal to or higher than the melting point of the second compound.
  • step (iii) may be repeated a plurality of times.
  • the number of repeated steps (iii) is not particularly limited.
  • the number of steps (iii) performed in the manufacturing method of the present disclosure may be in the range of 1 to 5 (for example, in the range of 2 to 3).
  • each of the plurality of steps (iii) may be the same or different.
  • the preparation conditions (components and concentrations, etc.) and drying conditions of the first aqueous dispersion in each step (iii) may be the same or different.
  • step (X) may be repeated a plurality of times.
  • the first layer (CL1) and the second layer (CL1) may be used as they are as the electrolyte layer.
  • the first layer (CL1) and the second layer (CL2) may be impregnated with the above-mentioned liquid component (L) to form an electrolyte layer.
  • the liquid component (L) may be impregnated after all the steps are completed.
  • the impregnation of the liquid component (L) may be performed, for example, by immersing the capacitor element precursor for which the step (iii) has been completed in the liquid component (L).
  • At least a part of the first compound precipitated on the surface of the constituent elements (anodose, etc.) of the capacitor element precursor by the step (ii) is dissolved in the first aqueous dispersion in the treatment of the step (iii-a). do.
  • a part of the first compound that was not dissolved in the first aqueous dispersion remains on the surface precipitated in step (ii).
  • most of the first compounds dissolved in the first aqueous dispersion remain in the vicinity of the surface. As a result, a portion where the first compound is unevenly distributed is generated in the vicinity of the surface.
  • the first compound present in the vicinity of the surface helps the first conductive polymer to adhere to the surface. Therefore, according to the above-mentioned production method, the amount of the first conductive polymer contained in the electrolyte layer can be increased, and high characteristics (for example, low ESR) can be achieved. Moreover, since the stability of the electrolyte layer can be improved, a highly reliable electrolytic capacitor can be obtained.
  • step (iii) when the impregnation step of the step (iii-a) is performed, the first conductive polymer filled in the capacitor element precursor by the previous step (iii) falls off. It is especially important to prevent this. Therefore, when the step (iii) is repeated, it is particularly important to perform the step (ii).
  • the electrolyte layer is formed. That is, as described above, the capacitor element including the electrolyte layer is formed.
  • the electrolytic capacitors (first and second electrolytic capacitors) of the present disclosure can be manufactured by using the capacitor elements obtained as described above.
  • the method for manufacturing an electrolytic capacitor using a capacitor element is not particularly limited, and a known method may be applied.
  • the capacitor element may be placed in a case and sealed.
  • the electrolytic capacitor of the present disclosure is not limited by the following figures.
  • the above-mentioned components can be applied to the components of the electrolytic capacitor of the example described below. Further, the components of the electrolytic capacitor of the example described below can be changed based on the above description. In addition, the matters described below may be applied to the above-described embodiment. The same parts may be designated by the same reference numerals and duplicate description may be omitted.
  • FIG. 1 schematically shows a cross section of an example of the electrolytic capacitor 100 of the first embodiment.
  • FIG. 2 shows a schematic view of a part of the capacitor element included in the electrolytic capacitor 100 shown in FIG.
  • the electrolytic capacitor 100 includes, for example, a capacitor element 10, a bottomed case 11 for accommodating the capacitor element 10, a sealing member 12 for closing the opening of the bottomed case 11, and a sealing member 12.
  • Lead tabs 15A and 15B (not shown) that connect the seat plate 13 that covers, the lead wires 14A and 14B that are led out from the sealing member 12 and penetrate the seat plate 13, and the lead wires 14A and 14B and the electrodes of the capacitor element 10.
  • the capacitor element 10 is housed in the bottomed case 11.
  • the liquid component (L) is also housed in the bottomed case 11.
  • the vicinity of the open end of the bottomed case 11 is drawn inward, and the open end of the bottomed case 11 is curled so as to crimp the sealing member 12.
  • the capacitor element 10 includes a foil-shaped anode body 21 having a dielectric layer on its surface, a foil-shaped cathode body 22, a separator 23 arranged between them, and an electrolyte layer (not shown).
  • the anode body 21 and the cathode body 22 are wound with the separator 23 arranged between them.
  • the outermost circumference of the winding body is fixed by the winding stop tape 24. Note that FIG. 2 shows a partially unfolded state before fixing the outermost circumference of the wound body.
  • FIG. 3 schematically shows a cross-sectional view of a part of an example of a capacitor element included in the first electrolytic capacitor.
  • the capacitor element 10a of FIG. 3 includes an anode body 21, a cathode body 22, and an electrolyte layer 31 and a separator (not shown) arranged between them.
  • a dielectric layer 21a is formed on the surface of the anode body 21.
  • the electrolyte layer 31 contains a first conductive polymer and a first compound. As described above, the electrolyte layer 31 includes an unevenly distributed portion (not shown) of the first compound.
  • the electrolyte layer 31 may contain the above-mentioned liquid component (L).
  • FIG. 4 schematically shows a cross-sectional view of a part of an example of a capacitor element included in the second electrolytic capacitor.
  • the capacitor element 10b of FIG. 4 includes an anode body 21, a cathode body 22, and an electrolyte layer 41 and a separator (not shown) arranged between them.
  • the electrolyte layer 41 includes a second layer 41b and a first layer 41a formed on at least the second layer 41b.
  • the arrangement of the electrolyte layer shown in FIG. 4 is an example, and the present disclosure is not limited to the arrangement shown in FIG.
  • the first layer 41a contains a first conductive polymer.
  • the second layer 41b contains a second conductive polymer.
  • the electrolyte layer 41 includes an unevenly distributed portion (not shown) of the first compound.
  • the electrolyte layer 41 may contain the above-mentioned liquid component (L).
  • capacitors A1 to A7 and capacitors C1 to C6 were prepared and evaluated.
  • the manufacturing method and evaluation method of these capacitors will be described below.
  • conditions different from the conditions of the above-mentioned steps (ii) and (iii) may be used, but for convenience, they are also used in the steps (ii) and (iii). It is explained as.
  • the capacitor A1 is a winding type electrolytic capacitor (diameter 10 mm ⁇ length 10 mm) having a rated voltage of 35 V and a rated capacitance of 270 ⁇ F.
  • the capacitor A1 was manufactured by the following procedure.
  • An Al foil having a thickness of 120 ⁇ m was prepared.
  • the Al foil was subjected to a direct current etching treatment to roughen the surface.
  • the Al foil was subjected to chemical conversion treatment to form a dielectric layer (thickness: about 70 nm) to obtain an anode body.
  • the dielectric layer was formed by immersing an Al foil in an ammonium adipate solution and performing a chemical conversion treatment at 70 ° C. for 5 hours while applying a voltage of 50 V to the Al foil.
  • the anode body of the capacitor A1 was prepared by cutting the anode body to a predetermined size.
  • Step (i)) An anode lead tab and a cathode lead tab to which a lead wire was connected were connected to the prepared anode body and cathode body, respectively. Then, the anode body and the cathode body were wound with a separator in between, and the outer surface was fixed with a winding stopper tape. As the separator, a non-woven fabric made of aramid (aromatic polyamide fiber), which is a synthetic fiber, was used. In this way, a wound body (capacitor element precursor) was produced. The prepared winding body was immersed in an ammonium adipate solution, and the anode body was subjected to chemical conversion treatment again at 70 ° C. for 60 minutes while applying a voltage of 50 V to the anode body. Formed a body layer.
  • aramid aromatic polyamide fiber
  • aqueous solution of mannitol having a concentration of 10% by mass was prepared by dissolving mannitol in ion-exchanged water.
  • the viscosity of the obtained aqueous mannitol solution was measured and found to be 5 mPa ⁇ s or less.
  • PEDOT polystyrene sulfonic acid
  • PEDOT: PSS polystyrene sulfonic acid
  • dispersion liquid in which PEDOT: PSS is dispersed may be referred to as "PEDOT: PSS dispersion liquid”.
  • a first aqueous dispersion having a PEDOT: PSS concentration of 2% by mass was prepared. The viscosity of the obtained dispersion was measured and found to be 25 mPa ⁇ s.
  • the first aqueous treatment liquid was placed in the container.
  • the wound body (capacitor element precursor) was immersed in the first aqueous treatment liquid in the container at room temperature under atmospheric pressure for 5 minutes.
  • the wound body was immersed in the first aqueous treatment liquid from the side to which the lead tab was not connected (the same applies to the other immersion steps described below).
  • the wound body was pulled up from the first aqueous treatment liquid.
  • the winding body was impregnated with the first aqueous treatment liquid.
  • the wound body was dried at 180 ° C. for 30 minutes in a drying oven, whereby the first aqueous treatment liquid was dried. In this way, the first compound was placed inside the winding body.
  • Step (iii) First, the first aqueous dispersion was placed in the container. Next, the winding body was immersed in the first aqueous dispersion in the container for 15 minutes in a reduced pressure atmosphere (40 kPa) at room temperature, and then the winding body was pulled up from the first aqueous dispersion. In this way, the winding body was impregnated with the first aqueous dispersion. Next, in the drying oven, the wound body was dried at 60 ° C. for 30 minutes, followed by drying at 125 ° C. for 15 minutes. As a result, the first aqueous dispersion was dried. In this way, the first layer (conductive polymer layer) was formed.
  • a reduced pressure atmosphere 40 kPa
  • step (iii) The wound body that had undergone step (iii) was impregnated with an electrolytic solution at room temperature under atmospheric pressure.
  • a solution mixed at a mass ratio of 25:25 was used. In this way, a capacitor element including an electrolyte layer was obtained. This capacitor element was sealed to complete an electrolytic capacitor. Then, while applying the rated voltage, the aging treatment was carried out at 150 ° C. for 1 hour. In this way, the capacitor A1 was obtained.
  • Capacitor A2 The capacitor A2 was manufactured under the same conditions as the capacitor A1 except that the separator was changed. A cellulose-based natural fiber non-woven fabric was used as the separator.
  • Step (X) was carried out as follows.
  • the PEDOT: PSS dispersion described in Fabrication of Capacitor A1 was used as the second aqueous dispersion. Using this second aqueous dispersion, impregnation and drying were carried out under the same conditions as in step (iii) of the capacitor A1 to form a second layer (conductive polymer layer). In this way, step (X) was performed. Then, the steps (ii) and (iii) were performed under the same conditions as the capacitor A1 to form the first layer on the second layer. After that, the capacitor A3 was manufactured in the same process as the capacitor A1.
  • Capacitor A4 The capacitor A4 was manufactured in the same manner as the capacitor A1 except that the step (X) described above was performed. Step (X) was carried out as follows.
  • a second aqueous dispersion was prepared by dissolving mannitol in the PEDOT: PSS dispersion described in Fabrication of Capacitor A1.
  • the concentration of PEDOT: PSS in the second aqueous dispersion was 2% by mass, and the concentration of mannitol was 10% by mass.
  • the viscosity of the obtained dispersion was measured and found to be 45 mPa ⁇ s.
  • step (iii) of the capacitor A1 Using this second aqueous dispersion, impregnation and drying were performed under the same conditions as in step (iii) of the capacitor A1 to form a second layer (conductive polymer layer). In this way, step (X) was performed. Then, the steps (ii) and (iii) were performed under the same conditions as the capacitor A1 to form the first layer on the second layer. After that, the capacitor A4 was manufactured in the same process as the capacitor A1.
  • Capacitor A5 The capacitor A5 was manufactured under the same conditions as the capacitor A1 except that the step (iii) of the capacitor A1 was performed twice in succession under the same conditions.
  • Capacitor A6 The capacitor A6 was produced in the same manner as the capacitor A1 except that the step (iii) was followed by another step (iii). Specifically, the capacitor A6 was produced by the following method.
  • the process (iii) of the capacitor A1 was performed. Then, another step (iii) was further performed.
  • the first aqueous dispersion the same one as the second aqueous dispersion (PEDOT: dispersion containing PSS and mannitol) used in the production of the capacitor A4 was used. Using this dispersion, impregnation and drying were performed under the same conditions as in step (iii) of the capacitor A1. After that, the capacitor A6 was manufactured in the same process as the capacitor A1.
  • Capacitor A7 The capacitor A7 was manufactured in the same manner as the capacitor A1 except that the steps (Y) and (X) were performed. Steps (Y) and (X) were carried out under the same conditions as in steps (ii) and (iii) of the capacitor A1, respectively. After forming the second layer in this way, the steps (ii) and (iii) were performed under the same conditions as those of the capacitor A1 to form the first layer on the second layer. After that, the capacitor A7 was manufactured in the same process as the capacitor A1.
  • Capacitor C1 The capacitor C1 was manufactured under the same conditions as the capacitor A1 except that the step (ii) was not performed.
  • Capacitor C2 The capacitor C1 was manufactured under the same conditions as the capacitor A1 except that the step (ii) was not performed and the dispersion liquid in the step (iii) was changed.
  • the dispersion liquid in step (iii) the same dispersion liquid as the second aqueous dispersion liquid (PEDOT: dispersion liquid containing PDS and mannitol) used in the production of the capacitor A4 was used.
  • PEDOT dispersion liquid containing PDS and mannitol
  • Capacitor C3 The capacitor C3 was manufactured under the same conditions as the capacitor A1 except that the step (ii) was not performed and the separator was different. As the separator, a separator made of the same natural fiber as the separator used in the capacitor A2 was used.
  • Capacitor C4 The capacitor C4 was manufactured under the same conditions as the capacitor A1 except that the step (ii) was not performed and the step (iii) was performed twice in succession.
  • Capacitor C5 The capacitor C5 is not subjected to the step (ii), and after the step (iii) is performed under conditions different from the step (iii) of the capacitor A1, the step (iii) is performed under the same conditions as the step (iii) of the capacitor A1. ), Except for the fact that the capacitor A1 was manufactured under the same conditions as the capacitor A1.
  • the first step (iii) is the same as the step (iii) of the capacitor A1 except that the second aqueous dispersion (PEDOT: dispersion containing PSS and mannitol) used in the production of the capacitor A4 is used. I went under the conditions.
  • PEDOT aqueous dispersion containing PSS and mannitol
  • the capacitor C6 is the capacitor A1 except that the step (ii) is not performed and the step (iii) is performed under the same conditions as the step (iii) of the capacitor A1 and then the step (iii) is performed under different conditions. It was prepared under the same conditions as above.
  • the second step (iii) is the same as the step (iii) of the capacitor A1 except that the second aqueous dispersion (PEDOT: dispersion containing PSS and mannitol) used in the production of the capacitor A4 is used. I went under the conditions.
  • the identification of the first compound (and the second compound described later) in the electrolyte layer and the distribution in the electrolyte layer can be examined by, for example, the following method.
  • the identification of the first compound can be carried out using a microscopic FT-IR analyzer (Nicollet-iN10 manufactured by Thermo Fisher).
  • a microscopic FT-IR analyzer Nicollet-iN10 manufactured by Thermo Fisher.
  • the electrolyte layer is divided into a plurality of parts, and the first compound existing in each part is extracted with an aqueous solvent.
  • the distribution of the first compound in each portion can be obtained.
  • ESR Equivalent series resistance
  • the breakdown withstand voltage was measured for the capacitors A1, A2, and C3. Specifically, a voltage was applied while boosting at a rate of 1.0 V / sec, and the breakdown withstand voltage through which an overcurrent of 0.5 A flowed was measured. Table 1 shows the measurement results and some of the manufacturing conditions for electrolytic capacitors.
  • "PEDOT: PSS mixture” means that the aqueous dispersion is a dispersion containing PEDOT: PSS and mannitol.
  • the drying in the step (ii-b) and the step (Yb) was carried out at 180 ° C. for 30 minutes. Further, the drying in the step (iii-b) and the step (X-b) was carried out under the conditions of 60 ° C. for 30 minutes and 125 ° C. for 15 minutes. Further, as described above, the viscosity of the mannitol aqueous solution is 5 mPa ⁇ s or less, the viscosity of the PEDOT: PSS dispersion is 25 mPa ⁇ s, and the viscosity of the dispersion containing PEDOT: PSS and mannitol is 45 mPa ⁇ s. there were. The melting point of mannitol is about 165 to 169 ° C.
  • the ESR value is preferably 15 m ⁇ or less (for example, in the range of 10 to 15 m ⁇ ), and more preferably 12 m ⁇ or less (for example, in the range of 8 to 12 m ⁇ ).
  • the breakdown withstand voltage is preferably high, and is preferably 70 V or higher (for example, in the range of 70 to 90 V). It is preferable that the reliability evaluation value F is small.
  • the evaluation value F is preferably 1.3 or less (for example, in the range of 1 to 1.3), and more preferably 1.2 or less (for example, in the range of 1 to 1.2).
  • the electrolytic capacitors (capacitors A1 to A7) of the present disclosure manufactured by the manufacturing method of the present disclosure performing the steps (ii) and (iii) exhibited high characteristics.
  • the capacitor A7 subjected to the step (Y) and the step (X) had particularly high characteristics.
  • the evaluation value F of the reliability of the capacitor A4 was lower. It is considered that this is because the capacitor A4 has unevenly distributed portions of the first compound near the surfaces of the anode foil and the cathode foil, and the thermal stability is improved.
  • This disclosure can be used for electrolytic capacitors and methods for manufacturing them.

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WO2025028056A1 (ja) * 2023-07-28 2025-02-06 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の製造方法

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