WO2023145889A1 - 電解コンデンサおよび電解コンデンサの製造方法 - Google Patents

電解コンデンサおよび電解コンデンサの製造方法 Download PDF

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Publication number
WO2023145889A1
WO2023145889A1 PCT/JP2023/002686 JP2023002686W WO2023145889A1 WO 2023145889 A1 WO2023145889 A1 WO 2023145889A1 JP 2023002686 W JP2023002686 W JP 2023002686W WO 2023145889 A1 WO2023145889 A1 WO 2023145889A1
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Prior art keywords
conductive polymer
polymer layer
electrolytic capacitor
separator
organic compound
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PCT/JP2023/002686
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English (en)
French (fr)
Japanese (ja)
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達治 青山
瞬平 松下
智之 田代
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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 US18/832,160 priority Critical patent/US20250182976A1/en
Priority to JP2023577032A priority patent/JPWO2023145889A1/ja
Priority to CN202380018836.1A priority patent/CN118633136A/zh
Publication of WO2023145889A1 publication Critical patent/WO2023145889A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • 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
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/04—Drying; Impregnating
    • 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
    • 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
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched 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
    • H01G9/145—Liquid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors
    • 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

Definitions

  • the present disclosure relates to electrolytic capacitors and methods of manufacturing electrolytic capacitors.
  • an electrolytic capacitor including a wound body of anode foil, separator, and cathode foil is known.
  • One example of such an electrolytic capacitor includes conductive polymer layers disposed in a winding.
  • the conductive polymer layer is formed, for example, by impregnating the wound body with a dispersion containing conductive polymer particles.
  • a dispersion containing conductive polymer particles has a high viscosity because it contains particles. Therefore, even if the wound body is impregnated with the dispersion, a sufficient conductive polymer layer may not be formed inside the wound body. Insufficient formation of the conductive polymer layer can cause a decrease in initial capacity, an increase in equivalent series resistance (ESR), a decrease in reliability, and the like.
  • ESR equivalent series resistance
  • the dielectric film formed on the surface of the anode foil is covered with dense conductive polymer particles, it becomes difficult for the electrolytic solution to come into contact with the surface of the dielectric layer. As a result, the dielectric layer (oxide film) forming function of the electrolytic solution is not sufficiently exhibited, which may cause an increase in leakage current or a short circuit.
  • Patent Literature 1 International Publication No. 2020/158780 describes "a step of preparing an electrode foil, and a step of preparing a first conductive polymer dispersion containing a first conductive polymer component and a first dispersion medium. and after applying the first conductive polymer dispersion to the surface of the electrode foil by a coating method, at least part of the first dispersion medium is removed, and the first conductive polymer component is included.
  • a method for manufacturing an electrolytic capacitor comprising the steps of: forming a first conductive polymer layer; and manufacturing a capacitor element using the electrode foil on which the first conductive polymer layer is formed.” disclosed.
  • Patent Document 2 International Publication No. 2020/158783 describes "a step of preparing an anode foil, a cathode foil and a fiber structure provided with a dielectric layer, and a conductive polymer containing a conductive polymer component and a dispersion medium.
  • preparing a dispersion applying the conductive polymer dispersion to the fibrous structure and then removing at least a portion of the dispersion medium to prepare a separator; and sequentially laminating the cathode foils to produce a capacitor element, wherein the dispersion medium contains water, the fiber structure contains 50% by mass or more of synthetic fiber, and the fiber structure contains A method for manufacturing an electrolytic capacitor, wherein the density is 0.2 g/cm 3 or more and less than 0.45 g/cm 3 .”
  • One object of the present disclosure is to provide a method for manufacturing an electrolytic capacitor that includes a conductive polymer layer and has high characteristics.
  • a first aspect of the present disclosure relates to a method for manufacturing an electrolytic capacitor.
  • the manufacturing method is a method for manufacturing an electrolytic capacitor including an anode foil having a dielectric layer formed thereon, a cathode foil, and a separator, wherein the surface of the dielectric layer and the surface of the cathode foil are selected from the surfaces of the dielectric layer and the cathode foil.
  • the polymer layer forming step includes a step (a) of applying a coating liquid containing the conductive polymer component and a liquid medium to the at least one surface and the separator; and (b) forming the conductive polymer layer on the at least one surface and the separator by removing a portion of the liquid medium from the coating liquid, wherein the liquid medium is water. and an organic compound that does not boil at 100° C. at 1 atmosphere, and in the step (b), part of the liquid medium is removed so that the organic compound remains in the conductive polymer layer.
  • the electrolytic capacitor includes a laminate including an anode foil having a dielectric layer formed thereon, a cathode foil, and a separator, and a liquid component impregnated in the laminate, wherein the laminate
  • the body includes a conductive polymer layer formed on at least one surface selected from the surface of the dielectric layer and the surface of the cathode foil and the separator, wherein the conductive polymer layer includes the at least There is a mixed region in which the first conductive polymer layer formed on one surface and the second conductive polymer layer formed on the separator are mixed, and the conductive polymer
  • the bed contains organic compounds that do not boil at 100° C. at 1 atmosphere.
  • an electrolytic capacitor including a conductive polymer layer and having high properties is obtained.
  • FIG. 1 is a side view schematically showing an electrolytic capacitor according to an embodiment of the present disclosure
  • FIG. 1 is an exploded perspective view schematically showing a capacitor element according to an embodiment of the present disclosure
  • FIG. 1 is an exploded perspective view schematically showing a capacitor element according to an embodiment of the present disclosure
  • a manufacturing method is a manufacturing method of an electrolytic capacitor including an anode foil having a dielectric layer formed thereon, a cathode foil, and a separator.
  • the manufacturing method may be hereinafter referred to as “manufacturing method (M)”.
  • the manufacturing method (M) includes a polymer layer forming step, a laminate forming step, and an impregnation step in this order. They are described below.
  • Polymer layer forming step In the polymer layer forming step, at least one surface selected from the surface of the dielectric layer (the dielectric layer on the surface of the anode foil) and the surface of the cathode foil and the separator are coated with a conductive high polymer component containing a conductive polymer component. This is the process of forming a molecular layer.
  • the at least one surface may hereinafter be referred to as "at least one surface (S)" or “surface (S)”.
  • the polymer layer forming step includes step (a) and step (b).
  • the step (a) is a step of applying a coating liquid containing a conductive polymer component and a liquid medium to the at least one surface (S) and the separator.
  • Step (b) is a step of forming a conductive polymer layer on at least one surface (S) and the separator by removing part of the liquid medium from the applied coating liquid.
  • the liquid medium includes water and organic compounds that do not boil at 100° C. at 1 atmosphere (101325 Pa). In step (b), part of the liquid medium is removed so that the organic compound remains in the conductive polymer layer. Step (a) and step (b) are described below.
  • the coating liquid may be applied to the surface of the dielectric layer and the separator, or the coating liquid may be applied to the surface of the cathode foil and the separator. Alternatively, the coating liquid may be applied to the surface of the dielectric layer, the surface of the cathode foil, and the separator. If necessary, a coating liquid is applied onto the dielectric layers formed on both sides of the anode foil, and a coating liquid is coated onto both sides of the cathode foil. A conductive polymer layer is formed at the location where the coating liquid is applied.
  • the conductive polymer component may be dispersed in the coating liquid in the form of particles.
  • Liquid media include water and organic compounds that do not boil at 100° C. at one atmosphere pressure.
  • the organic compound may be hereinafter referred to as "organic compound (C)".
  • the organic compound (C) may be one type of compound, or may be composed of a plurality of types of compounds. Therefore, the organic compound (C) can be read as "at least one organic compound".
  • the organic compound (C) is a compound that does not boil at 100° C. at 1 atmosphere. Therefore, by heating the coating liquid at a temperature at which the organic compound (C) does not boil or decompose and at a temperature of 100° C. or higher, water is removed from the coating liquid while the organic compound (C) can remain. . As a result, the organic compound (C) remains in the formed conductive polymer layer. If the organic compound (C) does not remain in the conductive polymer layer, the conductive polymer layer shrinks significantly when the liquid medium is removed from the coating liquid.
  • the liquid component eg, electrolytic solution
  • the dielectric layer (oxide film)-forming function of the liquid component is not sufficiently exhibited, which may cause an increase in leakage current or a short circuit.
  • step (b) part of the liquid medium is removed so that the organic compound (C) remains in the conductive polymer layer. Therefore, excessive shrinkage of the formed conductive polymer layer can be suppressed, and the impregnation property of the liquid component can be enhanced. As a result, according to the manufacturing method (M), an electrolytic capacitor including a conductive polymer layer and having high characteristics can be manufactured.
  • the method of applying the coating liquid is not limited, and it may be applied by a known method.
  • a method using a coater may be used, the coating liquid may be sprayed, or the object to be coated may be immersed in the coating liquid.
  • methods using a coater include gravure coating and die coating.
  • the method of applying the coating liquid to the separator includes a method of impregnating the separator with the coating liquid.
  • the coating liquid applied to the separator permeates into the separator, and a conductive polymer layer can be formed over the entire thickness of the separator.
  • the method for removing the liquid medium from the coating liquid is not limited as long as part of the liquid medium can be removed so that the organic compound (C) remains in the conductive polymer layer.
  • the liquid medium may be removed by heating and/or under reduced pressure, preferably at least by heating.
  • the heating temperature is preferably a temperature at which the organic compound (C) does not boil or decompose.
  • the heating temperature may be 100° C. or higher, 120° C. or higher, or 140° C. or higher, and may be 200° C. or lower, or 160° C. or lower.
  • the heating temperature may be in the range of 100°C to 200°C.
  • the heating time is not particularly limited as long as it can appropriately remove a part of the liquid medium. An example heating time is in the range of 5-60 minutes.
  • the step (b) may be performed by heating twice or more at a temperature within a predetermined range (for example, a temperature within a range of 100° C. to 200° C.). .
  • a temperature within a predetermined range for example, a temperature within a range of 100° C. to 200° C.
  • the conductive polymer layer is formed on the dielectric layers formed on both sides of the anode foil, one side is coated with the coating liquid and then heated, and the other side is coated with the coating liquid and then heated. may be performed.
  • a similar method can be applied when forming conductive polymer layers on both sides of the cathode foil.
  • the conductive polymer layer can be formed for each member. Therefore, the application of the coating liquid to one member (step (a)) may be performed after the drying treatment (step (b)) to another member. For example, after applying the coating liquid (step (a)) and drying treatment (step (b)) to the surface (S), applying the coating liquid to the separator (step (a)) and drying treatment (step (b)) may be performed.
  • steps (a) and (b) for forming a conductive polymer layer on the anode foil (on the dielectric layer) and a step for forming a conductive polymer layer on the cathode foil ( A) and step (b), and step (a) and step (b) for forming the conductive polymer layer on the separator can be performed in any order.
  • the water content in the coating liquid is 40% by mass or more (e.g., 50% by mass or more), and the amount of water in the conductive polymer layer is higher than that in the conductive polymer layer Steps (a) and (b) are carried out so that the mass of the organic compound (C) of is increased.
  • step (b) the ratio Ww/Wc between the mass Ww of water in the conductive polymer layer and the mass Wc of the organic compound (C) in the conductive polymer layer is 0 or more, or 0.1. 0.9 or less, or 0.95 or less.
  • Wc can be measured by a method described later.
  • Ww can be measured by Karl Fischer titration.
  • the ratio Wc/Wp of the mass Wc of the organic compound (C) remaining in the conductive polymer layer to the mass Wp of the conductive polymer component in the conductive polymer layer is 1.0 or more and 20 or less.
  • step (a) and step (b) may be performed.
  • the ratio Wc/Wp may be 1.0 or more, 1.2 or more, or 2.0 or more, and may be 20 or less, 12 or less, or 10 or less.
  • the ratio Wc/Wp may be 1.0 or more and 10 or less, 1.2 or more and 10 or less, or 2.0 or more and 10 or less.
  • a conductive polymer layer may be formed on the surface of the dielectric layer, the surface of the cathode foil, and the separator. According to this configuration, it is possible to form the conductive polymer layer continuously from the dielectric layer to the cathode foil facing the dielectric layer.
  • the conductive polymer layer formed on the surface (S) will be referred to as the "first conductive polymer layer”
  • the conductive polymer layer formed on the separator will be referred to as the “second conductive polymer layer.” sometimes referred to as a layer.
  • the second conductive polymer layer can be formed on the surface of the fibers or the microporous membrane that constitute the separator.
  • the first conductive polymer layer and the second conductive polymer layer may be composed of the same conductive polymer component, or may contain different conductive polymer components.
  • the first conductive polymer layer formed on the anode foil (on the dielectric layer), the first conductive polymer layer formed on the cathode foil, and the second conductive polymer layer are the same. It may be composed of a conductive polymer component, or may contain different conductive polymer components. In one preferred example, they contain the same conductive polymer component.
  • the first conductive polymer layer is formed on 80% or more (for example, 90% or more) of the surface area where the first conductive polymer layer is formed. It is preferable to form one conductive polymer layer.
  • the first conductive polymer layer is preferably formed on the entire surface of the electrode foil (anode foil, cathode foil) that contributes to the capacitance of the capacitor element.
  • the area where the second conductive polymer layer is formed on the separator is preferably 80% or more (for example, 90% or more) of the area of the separator, and may be formed on the entire separator.
  • the area of the surface of the electrode foil is an area not considering surface unevenness, and can be calculated from the outer shape of the electrode foil.
  • the area of the surface on which the first conductive polymer is formed is the sum of the areas of both sides.
  • the mass of the first conductive polymer layer per unit area may be 0.01 mg/cm 2 or more, or 0.02 mg/cm 2 or more, and 0.5 mg/cm 2 or less, or 0.3 mg. /cm 2 or less. By setting the mass to 0.1 mg/cm 2 or more, the conductive polymer layer can be formed more uniformly.
  • the mass per unit area is the mass of the layer formed on one side of the electrode foil.
  • the mass of the second conductive polymer layer per unit area may be 0.02 mg/cm 2 or more, or 0.05 mg/cm 2 or more, and 2.0 mg/cm 2 or less, or 1.0 mg. /cm 2 or less. By setting the mass to 0.3 mg/cm 2 or more, the conductive polymer layer can be formed more uniformly.
  • the mass of the conductive polymer layer per unit area can be obtained by the following method. First, a member (electrode foil or separator) before forming a conductive polymer layer is cut into five samples with a predetermined area, and the mass of the five samples is measured. In addition, five samples are prepared by cutting the member (electrode foil or separator) having the conductive polymer layer formed thereon into the predetermined area, and the mass of each sample is measured. Using the difference between the total mass of the five samples after the formation of the conductive polymer layer and the total mass of the five samples before the formation of the conductive polymer layer, and the predetermined area, the conductivity per unit area is calculated. The mass of the elastic polymer layer is determined.
  • the laminate forming step is a step of forming a laminate including a conductive polymer layer by laminating an anode foil, a cathode foil, and a separator such that the separator is disposed between the anode foil and the cathode foil. is.
  • the method of forming the laminate is not limited, and the laminate may be formed by a known method.
  • the laminate may be a wound body.
  • the wound body may be formed by winding the anode foil, the cathode foil, and the separator so that the separator is arranged between the anode foil and the cathode foil.
  • the anode foil, the cathode foil, and the separator are laminated in the radial direction of the wound body.
  • the laminate may be formed by unidirectionally laminating a flat anode foil, a flat cathode foil, and a flat separator.
  • a laminate may be formed by laminating a plurality of anode foils, a plurality of cathode foils, and a plurality of separators in one direction.
  • the anode foils and the cathode foils are arranged alternately, and the separator is arranged between the anode foils and the cathode foils.
  • the impregnation step is a step of impregnating the laminate formed by the laminate formation step with a liquid component.
  • the liquid component is hereinafter sometimes referred to as "liquid component (L)".
  • liquid component (L) There is no limitation on the method for impregnating the laminate with the liquid component (L).
  • the laminate may be impregnated with the liquid component (L) by immersing at least part of the laminate in the liquid component (L). Examples of the liquid component (L) will be described later.
  • a capacitor element including a conductive polymer layer and a liquid component is formed by the above steps. After that, the capacitor element is enclosed in the outer package as needed. Thus, an electrolytic capacitor is manufactured.
  • the manufacturing method (M) may include steps other than the above steps, if necessary.
  • the conductive polymer layer may include a first conductive polymer layer formed on the at least one surface (S) and a second conductive polymer layer formed on the separator.
  • the conductive polymer layer of the laminate that has undergone the impregnation step may have a mixed region where the first conductive polymer layer and the second conductive polymer layer are mixed. .
  • the liquid medium of the coating liquid is removed so that the organic compound (C) remains in the conductive polymer layer. Therefore, excessive shrinkage of the conductive polymer component is suppressed, and a mixed region in which the first conductive polymer layer and the second conductive polymer layer are mixed can be formed. . By forming the mixed region, it is possible to reduce the ESR of the capacitor element.
  • the coating liquid used in the polymer layer forming step contains the conductive polymer component, water, and the organic compound (C), as described above. If desired, the coating liquid may contain other components.
  • the organic compound (C) an organic compound that is easily dissolved in water can be preferably used.
  • the organic compound (C) may be a compound miscible with water.
  • examples of organic compounds (C) include compounds used as organic solvents.
  • Examples of organic compounds (C) include polyhydric alcohols having two or more hydroxyl groups. Water in which the organic compound (C) is dissolved can be used as a dispersion medium for the conductive polymer component. From one point of view, the coating liquid is a dispersion liquid in which particles of the conductive polymer component are dispersed, and the dispersion medium is water in which the organic compound (C) is dissolved.
  • organic compounds (C) include polyhydric alcohols, sulfolane, ⁇ -butyrolactone, and borate esters.
  • the organic compound (C) may contain at least one selected from the group consisting of polyhydric alcohols, sulfolane, ⁇ -butyrolactone, and borate esters, and may be at least one of them.
  • the organic compound (C) may contain at least one selected from the group consisting of glycols, glycerins, sugar alcohols, sulfolane, ⁇ -butyrolactone, and borate esters, and may be at least one of the .
  • polyhydric alcohols examples include glycols, glycerins, and sugar alcohols.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycol (eg, polyethylene glycol), polyoxyethylene polyoxypropylene glycol (ethylene oxide/propylene oxide copolymer), and the like.
  • glycerins include glycerin and polyglycerin.
  • sugar alcohols include mannitol, xylitol, sorbitol, erythritol, pentaerythritol, and the like.
  • the boiling point means the boiling point at 1 atm unless otherwise specified.
  • organic compounds (C) include organic compounds with a boiling point higher than 100°C.
  • the boiling point may be 110° C. or higher, 150° C. or higher, or 200° C. or higher; There may be.
  • the boiling point may be in the range of 110°C to 400°C (eg, in the range of 150°C to 350°C).
  • the conductive polymer component may contain a conductive polymer or be composed of only a conductive polymer.
  • the conductive polymer component may contain a conductive polymer and a dopant.
  • Examples of conductive polymers include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, and derivatives thereof. Such derivatives include polymers having polypyrrole, polythiophene, polyfuran, polyaniline, and polyacetylene as basic skeletons.
  • derivatives of polythiophene include poly(3,4-ethylenedioxythiophene) and the like. These conductive polymers may be used alone or in combination.
  • the conductive polymer may be a copolymer of two or more monomers.
  • the weight average molecular weight of the conductive polymer is not particularly limited, and may be in the range of 1,000 to 100,000, for example.
  • a preferred example of a conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT).
  • the conductive polymer may be doped with a dopant.
  • a polymer dopant As the dopant.
  • polymeric dopants include polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, Polyacrylic acid and the like are included. These may be used alone or in combination of two or more. At least part of these may be added in the form of salts.
  • a preferred example of a dopant is polystyrene sulfonic acid (PSS).
  • the dopant may be a dopant containing an acidic group or a polymer dopant containing an acidic group.
  • acidic groups include sulfonic acid groups, carboxyl groups, and the like.
  • a polymeric dopant containing an acidic group is a macromolecule (polymer) in which at least some of the constitutional units contain an acidic group. Examples of such polymeric dopants include the polymeric dopants described above.
  • the weight average molecular weight of the dopant is not particularly limited. From the viewpoint of facilitating the formation of a homogeneous conductive polymer layer, the dopant may have a weight average molecular weight in the range of 1,000 to 100,000.
  • the dopant may be polystyrene sulfonic acid
  • the conductive polymer may be poly(3,4-ethylenedioxythiophene). That is, the conductive polymer component may be poly(3,4-ethylenedioxythiophene) doped with polystyrenesulfonic acid.
  • the pH of the coating liquid is preferably less than 7.0, preferably 6.0 or less or 5.0 or less, in order to suppress dedoping of the dopant. good too.
  • the pH of the coating liquid may be 1.0 or higher, or 2.0 or higher.
  • the conductive polymer component may exist in the coating liquid in the form of particles.
  • the mode of particle size may be 10 nm or more, or 20 nm or more, and may be 1000 nm or less, 500 nm or less, 200 nm or less, or 100 nm or less. good.
  • the volume-based particle size distribution can be determined using a laser diffraction/scattering particle size distribution analyzer.
  • the mode of the particle size of the particles of the conductive polymer component may be in the range of 20 nm to 200 nm (for example, in the range of 20 nm to 100 nm). Further, in the volume-based particle size distribution, the volume-based proportion of particles having a particle diameter in the range of 20 nm to 100 nm may be 90% or more of the whole. These ranges make it easier to form a conductive polymer layer containing a conductive polymer component in the pores of the members (electrode foil and separator).
  • the water content in the coating liquid is 40% by mass or more, 50% by mass or more, 70% by mass or more, 73% by mass or more, 78% by mass or more, 80% by mass or more, 88% by mass or more, 90% by mass or more, or It may be 95% by mass or more.
  • the content may be 98% by mass or less, 95% by mass or less, 90% by mass or less, or 80% by mass or less.
  • the content may be in the range of 40-98% by weight or more, in the range of 50-98% by weight, in the range of 80-98% by weight, or in the range of 70-98% by weight. In any of these ranges, the upper limit may be replaced by 95 wt%, 90 wt%, or 80 wt%.
  • the content of the organic compound (C) in the coating liquid may be 1.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, or 10% by mass or more.
  • the content may be 59.5% by mass or less, 45% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
  • the content may be in the range of 1-59.5% by weight, in the range of 3-59.5% by weight, or in the range of 5-59.5% by weight. In any of these ranges, the upper limit may be replaced by 45 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, or 10 wt%.
  • the content of the conductive polymer component in the coating liquid may be 0.5% by mass or more, or 1.0% by mass or more, and may be 4.0% by mass or less, 3.0% by mass or less, or 2. It may be 0% by mass or less.
  • the content may be in the range of 0.5 to 4.0% by mass, or in the range of 1.0 to 4.0% by mass. In any of these ranges, the upper limit may be 3.0 wt% or 2.0 wt%.
  • the content is preferably in the range of 1.0 to 3.0% because the physical properties of the coating liquid and its stability over time are excellent, and the balance between the ESR and the cost of the electrolytic capacitor is good. preferable.
  • the coating liquid contains a dopant
  • the mass of the dopant is included in the mass of the conductive polymer component.
  • the mass of the dopant contained in the coating liquid is not particularly limited, and may be in the range of 0.1 to 5 times (for example, the range of 0.5 to 3 times) the mass of the conductive polymer contained in the coating liquid. .
  • water content: organic compound (C) content: conductive polymer component content 40 to 98: 1.0 to 59.5: 0.5 to 4.0
  • the ratio of water content: organic compound (C) content: conductive polymer component content ratio may be 69.5 to 98: 1.0 to 30: 0.5 to 4.0.
  • the content of water, the content of the organic compound (C), and the content of the conductive polymer component can be arbitrarily combined as long as there is no contradiction.
  • An example of the coating liquid may satisfy one, two, three, or four conditions arbitrarily selected from the following conditions (1) to (5), or may satisfy all conditions. .
  • the content of water is in the range of 50 to 98% by mass (eg, the range of 73 to 95% by mass), and the content of the organic compound (C) is in the range of 3 to 30% by mass (eg, 5 to 25% by mass). range), and the content of the conductive polymer component is in the range of 0.5 to 4.0% by mass (for example, in the range of 1.0 to 3.0% by mass).
  • Organic compound (C) is a glycol (eg, ethylene glycol).
  • the conductive polymer component contains poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid.
  • the conductive polymer component may be composed of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid.
  • the pH of the coating liquid is in the range of 1.0 to 6.0 (for example, the range of 2.0 to 5.0).
  • the conductive polymer component is present in the coating liquid in the form of particles, and in the volume-based particle size distribution of the particles of the conductive polymer component, the mode of the particle size is in the range of 20 nm to 1000 nm (for example, 20 nm to 200 nm or 20 nm to 100 nm).
  • the proportion (volume-based) of particles having a particle size in the range of 20 nm to 1000 nm (for example, the range of 20 nm to 200 nm or the range of 20 nm to 100 nm) to the total particles is 90% or more. There may be.
  • the coating liquid may satisfy the above conditions (3) and (4). By satisfying the conditions (3) and (4), a highly conductive conductive polymer layer can be formed.
  • liquid component (L) examples of the liquid component (L) used in the impregnation step include non-aqueous solvents and electrolytic solutions.
  • An electrolytic solution containing a non-aqueous solvent and a solute dissolved in the non-aqueous solvent can be used as the electrolytic solution.
  • the liquid component (L) may be a component that is liquid at room temperature (25° C.) or a component that is liquid at the temperature at which the electrolytic capacitor is used. .
  • the non-aqueous solvent used for the liquid component (L) may be an organic solvent, an ionic liquid, or a protic solvent.
  • 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- 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 methyl ethyl ketone, and formaldehyde. .
  • a polymer-based solvent may be used as the non-aqueous solvent.
  • polymer solvents include polyalkylene glycol, derivatives of polyalkylene glycol, compounds in which at least one hydroxyl group in a polyhydric alcohol is substituted with polyalkylene glycol (including derivatives), and the like.
  • polymer solvents examples include polyethylene glycol (PEG), polyethylene glycol glyceryl ether, polyethylene glycol diglyceryl ether, polyethylene glycol sorbitol ether, polypropylene glycol, polypropylene glycol glyceryl ether, polypropylene glycol diglyceryl ether, Polypropylene glycol sorbitol ether, polybutylene glycol and the like are included.
  • polymer solvents further include ethylene glycol-propylene glycol copolymers, ethylene glycol-butylene glycol copolymers, propylene glycol-butylene glycol copolymers, and the like.
  • the non-aqueous solvents may be used singly or in combination of two or more.
  • the liquid component (L) may contain a non-aqueous solvent and a base component (base) dissolved in the non-aqueous solvent.
  • the liquid component (L) may also contain a non-aqueous solvent and a base component and/or an acid component (acid) dissolved in the non-aqueous solvent.
  • Polycarboxylic acids and monocarboxylic acids can be used as the acid component.
  • examples of the above polycarboxylic acids include aliphatic polycarboxylic acids ([saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 ,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid]; [unsaturated polycarboxylic acids such as maleic acid, fumaric acid, icotanic acid]), aromatic polycarboxylic acids (e.g.
  • phthalic acid isophthalic acid, terephthalic acid , trimellitic acid, pyromellitic acid
  • alicyclic polycarboxylic acids eg, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, etc.
  • Examples of the above monocarboxylic acids include aliphatic monocarboxylic acids (having 1 to 30 carbon atoms) ([saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, behenic acid]; [unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, oleic acid]), aromatic monocarboxylic acids (e.g. benzoic acid, cinnamic acid, naphthoic acid), oxycarboxylic acids (eg salicylic acid, mandelic acid, resorcinic acid).
  • saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, capro
  • maleic acid, phthalic acid, benzoic acid, pyromellitic acid, and resorcinic acid are thermally stable and are preferably used.
  • An inorganic acid may be used as the acid component.
  • representative inorganic acids include phosphoric acid, phosphorous acid, hypophosphorous acid, alkyl phosphates, boric acid, borofluoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, benzenesulfonic acid, and naphthalene sulfone. acid and the like.
  • the base component may be a compound having an alkyl-substituted amidine group, such as an imidazole compound, a benzimidazole compound, or an alicyclic amidine compound (pyrimidine compound, imidazoline compound).
  • an imidazole compound such as an imidazole compound, a benzimidazole compound, or an alicyclic amidine compound (pyrimidine compound, imidazoline compound).
  • 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5 1,2-dimethylimidazolinium, 1,2, 4-trimethylimidazoline, 1-methyl-2-ethyl-imidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl-2-heptylimidazoline, 1-methyl-2-(3'heptyl)imidazoline, 1- Methyl-2-dodecylimidazoline, 1,2-
  • a quaternary salt of a compound having an alkyl-substituted amidine group may be used as the base component.
  • Examples of such basic components include imidazole compounds, benzimidazole compounds, and alicyclic amidine compounds (pyrimidine compounds, imidazoline compounds) quaternized with an alkyl group or arylalkyl group having 1 to 11 carbon atoms. be done.
  • a tertiary amine may also be used as the base component.
  • tertiary amines include trialkylamines (trimethylamine, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, dimethylisopropylamine, methylethyln-propylamine, methylethylisopropylamine, diethyl-n- propylamine, diethylisopropylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, etc.), phenyl group-containing amines (dimethylphenylamine, methylethylphenylamine, diethylphenylamine, etc.
  • trialkylamines are preferable in terms of high conductivity, and it is more preferable to include at least one selected from the group consisting of trimethylamine, dimethylethylamine, methyldiethylamine, and triethylamine.
  • secondary amines such as dialkylamines, primary amines such as monoalkylamines, and ammonia may be used.
  • the liquid component (L) may contain a salt of an acid component and a base component.
  • Salts may be inorganic and/or organic salts.
  • An organic salt is a salt in which at least one of the anion and cation contains an organic substance. Examples of organic salts include trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono-1,2,3,4-tetramethylimidazolinium phthalate, mono-1,3-dimethyl-2-phthalate, Ethylimidazolinium and the like may also be used.
  • the pH of the liquid component (L) may be less than 7.0 or 5.0 or less, or may be 1.0 or more, or 2.0 or more.
  • the pH may be 1.0 or more and less than 7.0 (for example, in the range of 2.0 to 5.0).
  • the liquid component (L) preferably contains a protic solvent. A high effect is obtained when the liquid component (L) contains a protic solvent.
  • the liquid component (L) may contain a solvent other than the protic solvent in addition to the protic solvent.
  • the protic solvent may contain at least one selected from the group consisting of glycols, glycerin, polyglycerin, and sugar alcohols, and may be at least one of them.
  • the protic solvent may be composed of only one type of compound, or may contain multiple types of compounds.
  • the organic compound (C) and the liquid component (L) may contain the same compound.
  • they may contain the same polyhydric alcohols, they may contain the same glycols (such as ethylene glycol), they may contain the same sugar alcohols.
  • a liquid containing water as a main component and a second organic compound that does not boil at 100° C. at 1 atm is applied to the laminate.
  • a liquid containing water as the main component and a second organic compound that does not boil at 100 ° C. at 1 atmosphere is laminated. a first step of impregnating the conductive polymer layer in the body; and a second step of removing part of the liquid impregnated in the flexible polymer layer in this order.
  • the above organic compound (C) be the first organic compound.
  • the first organic compound and the second organic compound may be the same or different.
  • the compounds exemplified for the organic compound (C) may be used as the second organic compound.
  • the liquid used in the first step the coating liquid used in the polymer layer forming step may be used, or the liquid obtained by removing the conductive polymer component from the coating liquid may be used.
  • the first step may be carried out in the manner described for step (a).
  • the second step may be carried out in the manner described for step (b). Adhesion between the first conductive polymer layer and the second conductive polymer layer can be increased by the step of impregnating the conductive polymer layer with the liquid.
  • An electrolytic capacitor according to an embodiment of the present disclosure may be hereinafter referred to as an “electrolytic capacitor (E)”.
  • the electrolytic capacitor (E) can be manufactured by the manufacturing method (M).
  • the electrolytic capacitor (E) may be manufactured by a method other than the manufacturing method (M). Since the matters described for the manufacturing method (M) can also be applied to the electrolytic capacitor (E), redundant description may be omitted. Also, the matters described for the electrolytic capacitor (E) may be applied to the manufacturing method (M).
  • the electrolytic capacitor (E) includes a laminate including an anode foil having a dielectric layer formed on its surface, a cathode foil, and a separator, and a liquid component impregnated in the laminate.
  • the liquid component is the liquid component (L) described above.
  • the laminate includes a conductive polymer layer formed on at least one surface (S) selected from the surface of the dielectric layer and the surface of the cathode foil and the separator. In the conductive polymer layer, a mixed region in which the first conductive polymer layer formed on at least one surface (S) and the second conductive polymer layer formed on the separator are mixed. exists.
  • An organic compound (C) that does not boil at 100° C. at 1 atm is present in the conductive polymer layer (for example, mixed region).
  • the mixed region can be formed by manufacturing the electrolytic capacitor (E) with the manufacturing method (M). In that case, the organic compound (C) present in the mixed region is contained in the coating liquid used in step (a).
  • the electrolytic capacitor (E) includes a mixed region, ESR can be reduced. Further, by manufacturing the electrolytic capacitor (E) by the manufacturing method (M), the above effects can be obtained.
  • the organic compound (C) present in the mixed region may contain at least one selected from the group consisting of polyhydric alcohol, sulfolane, ⁇ -butyrolactone, and borate ester, and the at least one may be
  • the laminate is impregnated with the liquid component (L).
  • the electrolytic capacitor (E) may contain at least one selected from the group consisting of glycols, glycerin, polyglycerin, and sugar alcohols in the laminate (for example, the mixed region). According to this configuration, the adhesion between the first conductive polymer layer and the second conductive polymer layer is enhanced.
  • An example of the configuration and components of the electrolytic capacitor (E) manufactured by the manufacturing method (M) is described below.
  • An example electrolytic capacitor described below includes a capacitor element, an outer casing, an anode lead terminal, and a cathode lead terminal.
  • the configuration and components of the electrolytic capacitor (E) are not limited to the following examples.
  • the electrolytic capacitor (E) includes a laminate and a liquid component (L) impregnated in the laminate.
  • the laminate includes a conductive polymer layer.
  • the laminate functions as a capacitor element.
  • the laminate includes an anode foil having a dielectric layer formed thereon, a cathode foil, and a separator.
  • the electrolytic capacitor (E) usually includes an outer package in which the laminate is enclosed.
  • anode foil examples include metal foils containing at least one of valve action metals such as titanium, tantalum, aluminum and niobium, and may be metal foils of valve action metals (eg, aluminum foil).
  • the anode foil may contain the valve metal in the form of an alloy containing the valve metal or a compound containing the valve metal.
  • the thickness of the anode foil may be 15 ⁇ m or more and 300 ⁇ m or less.
  • the surface of the anode foil may be roughened by etching or the like.
  • a dielectric layer is formed on the surface of the anode foil.
  • the dielectric layer may be formed by chemically converting the anode foil.
  • the dielectric layer may include a valve metal oxide (eg, aluminum oxide). It should be noted that the dielectric layer may be formed of a dielectric other than oxides of valve metals as long as it functions as a dielectric.
  • the conductive polymer layer may not be formed on the end face of the anode foil.
  • cathode foil The cathode foil is not particularly limited as long as it functions as a cathode.
  • cathode foils include metal foils (eg aluminum foils).
  • the type of metal is not particularly limited, and may be a valve action metal or an alloy containing a valve action metal.
  • the thickness of the cathode foil may be 15 ⁇ m or more and 300 ⁇ m or less.
  • the surface of the cathode foil may be roughened or chemically treated as necessary.
  • the cathode foil may include a conductive coating layer.
  • the coating layer may contain at least one metal having a lower ionization tendency than carbon and the valve action metal. This makes it easier to improve the acid resistance of the metal foil.
  • the coating layer may contain at least one selected from the group consisting of carbon, nickel, titanium, tantalum and zirconium. Among other things, the coating layer may comprise nickel and/or titanium due to their low cost and low resistance.
  • the thickness of the coating layer may be 5 nm or more, 10 nm or more, or 200 nm or less.
  • the coating layer may be formed by vapor-depositing or sputtering the metal on the metal foil. Alternatively, the coating layer may be formed by vapor-depositing a conductive carbon material or applying a carbon paste containing a conductive carbon material to the metal foil. Examples of conductive carbon materials include graphite, hard carbon, soft carbon, carbon black, and the like.
  • a porous sheet can be used as the separator.
  • porous sheets include wovens, nonwovens, and microporous membranes.
  • the thickness of the separator is not particularly limited, and may be in the range of 10-300 ⁇ m.
  • separator materials include cellulose, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, vinylon, nylon, aromatic polyamide, polyimide, polyamideimide, polyetherimide, rayon, glass, and the like.
  • the exterior body includes a case and/or sealing resin.
  • the sealing resin may contain a thermosetting resin.
  • thermosetting resins include epoxy resins, phenolic resins, silicone resins, melamine resins, urea resins, alkyd resins, polyurethanes, polyimides, unsaturated polyesters, and the like.
  • the encapsulating resin may contain fillers, curing agents, polymerization initiators, and/or catalysts.
  • FIG. 1 is a cross-sectional view schematically showing an example electrolytic capacitor 100 according to this embodiment.
  • FIG. 2 is a schematic diagram in which a part of the capacitor element 10 included in the electrolytic capacitor 100 is expanded.
  • the electrolytic capacitor 100 includes a capacitor element 10, a bottomed case 101 that accommodates the capacitor element 10, a sealing member 102 that closes an opening of the bottomed case 101, a seat plate 103 that covers the sealing member 102, and a sealing member.
  • Lead wires 104A and 104B lead out from 102 and pass through seat plate 103, and lead tabs 105A and 105B connecting the lead wires and electrodes of capacitor element 10 are provided.
  • the vicinity of the open end of the bottomed case 101 is drawn inward, and the open end is curled so as to be crimped to the sealing member 102 .
  • the capacitor element 10 is, for example, a wound body as shown in FIG.
  • the wound body includes anode foil 11 connected to lead tab 105A, cathode foil 12 connected to lead tab 105B, and separator 13 .
  • Capacitor element 10 (wound body) includes a conductive polymer layer (not shown).
  • the conductive polymer layer contains an organic compound (C).
  • the electrolytic capacitor 100 includes a liquid component (L) (for example, electrolyte) impregnated in the capacitor element 10 .
  • FIG. 1 shows a partially unfolded state before stopping the outermost circumference of the wound body.
  • the electrolytic capacitor should have at least one capacitor element, and may have a plurality of capacitor elements.
  • the number of capacitor elements included in the electrolytic capacitor may be determined according to the application.
  • Capacitor A1 An electrolytic capacitor (capacitor A1) was produced by the following method.
  • (a) Preparation of Components An aluminum foil (thickness: 100 ⁇ m) was subjected to an etching treatment to roughen the surface of the aluminum foil. The surface of the roughened aluminum foil was chemically treated to form a dielectric layer. Thus, an anode foil having dielectric layers formed on both sides was obtained.
  • An aluminum foil (thickness: 50 ⁇ m) was etched to roughen the surface of the aluminum foil to obtain a cathode foil.
  • a nonwoven fabric (50 ⁇ m thick) was prepared as a separator.
  • the nonwoven fabric is composed of 50% by mass of synthetic fibers (25% by mass of polyester fiber, 25% by mass of aramid fiber) and 50% by mass of cellulose, and contains polyacrylamide as a paper strength agent.
  • the density of the nonwoven fabric was 0.35 g/cm 3 .
  • a dispersion liquid (commercial product) was prepared by dispersing particles of polyethylenedioxythiophene (PEDOT) doped with polystyrene sulfonic acid (PSS) in water. Ethylene glycol (organic compound (C)) and water were added to this dispersion to obtain a coating liquid.
  • the ratio of each component in the coating liquid was the ratio shown in Table 1 below.
  • a conductive polymer layer was formed on both sides of the cathode foil by the same method as that formed on both sides of the anode foil.
  • a conductive polymer layer was formed on the separator by applying the coating liquid to the separator and then performing a drying treatment in the same manner as the method for forming on both sides of the anode foil.
  • Capacitor Element (d) Fabrication of Capacitor Element
  • the anode foil, cathode foil, and separator were each cut into predetermined sizes.
  • An anode lead tab and a cathode lead tab were connected to the anode foil and the cathode foil.
  • the anode foil and the cathode foil were wound with a separator interposed therebetween.
  • An anode lead wire and a cathode lead wire were connected to the end of each lead tab protruding from the wound body.
  • the resulting wound body was subjected to chemical conversion treatment again to form a dielectric layer on the end face of the anode foil.
  • the ends of the outer surface of the wound body were fixed with a winding stop tape to obtain a capacitor element.
  • Impregnation of Liquid Component An electrolytic solution (liquid component) was prepared by dissolving o-phthalic acid and triethylamine (base component) in ethylene glycol (solvent) at a total concentration of 25% by mass. The capacitor element was immersed in the electrolytic solution for 5 minutes in a reduced pressure atmosphere (40 kPa). Thus, the capacitor element (laminate) was impregnated with the electrolytic solution.
  • Electrolytic capacitors (capacitors A2 to A24 and C1) were produced in the same manner as capacitor A1, except that the composition of the coating liquid was changed.
  • the composition of the coating liquid was changed as shown in Table 1 below. Specifically, the type of organic compound (C) and/or the ratio of components were changed as shown in Table 1.
  • the drying conditions for forming the conductive polymer layer were set to 135° C. for 30 minutes. The produced capacitors were evaluated by the following methods.
  • the ratio Wc/Wp between the mass Wc of the organic compound (C) remaining in the conductive polymer layer and the mass Wp of the conductive polymer component in the conductive polymer layer is determined. rice field.
  • the mass Wp is the concentration of the conductive polymer component in the dispersion (coating liquid) containing the conductive polymer component used when forming the conductive polymer layer on the anode foil, and the concentration of the conductive polymer layer. can be calculated from the mass of the dispersion liquid used to form the
  • the mass Wc is calculated according to the following procedure. First, after a dispersion containing a conductive polymer component and a liquid medium (in this example, the organic compound (C) and water) is applied to the anode foil, a part of the liquid medium is removed from the applied dispersion. Measure the mass W0 (initial) of the capacitor element before the part is removed. Next, the mass W1 (after treatment) of the anode foil after part of the liquid medium is removed is measured. Then, the mass Wc can be calculated from the mass difference (W1-W0) between the post-treatment mass W1 and the initial mass W0. In this example, it is believed that most of the water in the dispersion applied to the anode foil is removed by the drying process.
  • a liquid medium in this example, the organic compound (C) and water
  • the mass difference (W1-W0) was regarded as the mass Wc of the organic compound (C).
  • the mass Ww of water remaining in the conductive polymer layer may be obtained by Karl Fischer titration, and (W1-W0-Ww) may be Wc.
  • Adhesion between anode foil and separator Adhesion between the anode foil and the separator was evaluated using a peel tester.
  • ESR Equivalent series resistance
  • LC leakage current
  • Tables 1 and 2 show the composition of the coating liquid used to manufacture the electrolytic capacitor and the evaluation results.
  • "#200”, “#300”, “#400”, and “#2000” in Table 2 indicate that the weight average molecular weights are about 200, about 300, about 400, and about 2000, respectively. .
  • Capacitor element 11 Anode foil 12: Cathode foil 13: Separator 14: Winding tape 100: Electrolytic capacitor 101: Bottomed case 102: Sealing member 103: Seat plate 104A, 104B: Lead wire 105A, 105B: Lead tab

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JP2019516241A (ja) * 2016-04-11 2019-06-13 ケメット エレクトロニクス コーポレーション ハイブリッドコンデンサ及びコンデンサの製造方法
JP2017216317A (ja) * 2016-05-31 2017-12-07 信越ポリマー株式会社 キャパシタ用導電性高分子分散液、キャパシタ及びその製造方法

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