WO2025028067A1 - 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
WO2025028067A1
WO2025028067A1 PCT/JP2024/022727 JP2024022727W WO2025028067A1 WO 2025028067 A1 WO2025028067 A1 WO 2025028067A1 JP 2024022727 W JP2024022727 W JP 2024022727W WO 2025028067 A1 WO2025028067 A1 WO 2025028067A1
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Prior art keywords
conductive polymer
polymer layer
electrolytic capacitor
separator
layer
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English (en)
French (fr)
Japanese (ja)
Inventor
由起也 下山
信太郎 脇山
瞬平 松下
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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 JP2025537728A priority Critical patent/JPWO2025028067A1/ja
Priority to CN202480048675.5A priority patent/CN121569359A/zh
Publication of WO2025028067A1 publication Critical patent/WO2025028067A1/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
    • 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
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • 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

Definitions

  • This disclosure relates to electrolytic capacitors and methods for manufacturing electrolytic capacitors.
  • a known electrolytic capacitor is one that includes a wound body of an anode foil, a separator, and a cathode foil.
  • One example of such an electrolytic capacitor includes a conductive polymer layer disposed in the wound body.
  • the conductive polymer layer can be formed by impregnating the wound body with a dispersion liquid that contains a conductive polymer.
  • Various proposals have been made in the past regarding electrolytic capacitors that include a conductive polymer layer.
  • Patent document 1 JP Patent Publication 2022-144278 A describes in claim 1, "A solid electrolytic capacitor comprising a capacitor element formed by opposing an anode foil and a cathode body, a conductive polymer layer formed by impregnating a dispersion containing conductive polymer particles or powder and a solvent, and an electrolyte impregnated into the capacitor element, the cathode body being made of a valve metal, a cathode foil having a surface expansion layer formed on its surface, and a carbon layer laminated on the surface expansion layer and in contact with the conductive polymer layer on the opposite side to the surface expansion layer, the amount of the conductive polymer particles or powder contained in the surface expansion layer being less than the amount of the conductive polymer particles or powder contained in the surface layer side of the carbon layer facing the conductive polymer layer.”
  • Claim 1 of Patent Document 2 JP Patent Publication No. 2019-516241 describes a "capacitor including a processing element, the processing element including: an anode including a dielectric on a surface and an anode conductive polymer layer on the surface of the dielectric; a cathode including a cathode conductive polymer layer; a conductive separator between the anode and the cathode; an anode lead in electrical contact with the anode; and a cathode lead in electrical contact with the cathode.”
  • Claim 1 of Patent Document 3 describes a hybrid electrolytic capacitor comprising: a cathode having a cathode substrate made of a valve metal, an oxide layer made of an oxide of the valve metal provided on the surface of the cathode substrate, an inorganic conductive layer containing an inorganic conductive material provided on the surface of the oxide layer, and an organic conductive layer containing a conductive polymer provided on the surface of the inorganic conductive layer; an anode having an anode substrate made of a valve metal, and a dielectric layer made of an oxide of the valve metal constituting the anode substrate provided on the surface of the anode substrate; a solid electrolyte layer provided between the organic conductive layer of the cathode and the dielectric layer of the anode and containing conductive polymer particles in contact with them, and an electrolyte filled between the conductive polymer particles in the solid electrolyte layer.
  • JP 2022-144278 A Special Publication No. 2019-516241 International Publication No. 2021/125182
  • the laminate includes an anode foil having a dielectric layer on its surface, a cathode foil having an inorganic layer on its surface, a separator, and a first conductive polymer layer held by the separator.
  • the first conductive polymer layer contains a first conductive polymer, and the ratio of the area of the first conductive polymer layer to the area of the surface of the separator is 80% or more.
  • the first conductive polymer layer held by the separator is in close contact with the inorganic layer.
  • the manufacturing method includes a preparation step of preparing an anode foil having a dielectric layer on its surface and a cathode foil having an inorganic layer on its surface, a first polymer layer formation step of forming a first conductive polymer layer in the gap of a separator, a laminate formation step of forming a laminate including the anode foil, the cathode foil, and the separator disposed between the anode foil and the cathode foil, and an adhesion step of adhering the first conductive polymer layer to the inorganic layer by impregnating the laminate with a liquid containing an organic solvent.
  • the first polymer layer formation step includes a first coating liquid application step of applying a first coating liquid containing a first conductive polymer and a first liquid medium into the gap of the separator, and a first liquid medium removal step of forming the first conductive polymer layer in the gap of the separator by removing at least a part of the first liquid medium from the first coating liquid.
  • an electrolytic capacitor containing a liquid component and a conductive polymer layer and having a low equivalent series resistance (ESR) can be obtained.
  • FIG. 1 is a side view illustrating a schematic diagram of an example of an electrolytic capacitor according to an embodiment of the present disclosure.
  • FIG. 2 is an exploded perspective view illustrating a schematic diagram of an example of a capacitor element according to an embodiment of the present disclosure.
  • FIG. 3 is a schematic diagram showing an example of a peel strength measuring device.
  • the dispersion liquid containing the conductive polymer has a high viscosity, even if the dispersion liquid is impregnated into the wound body, it may not be possible to form a sufficient conductive polymer layer inside the wound body. Insufficient formation of the conductive polymer layer can cause an increase in equivalent series resistance (ESR).
  • ESR equivalent series resistance
  • This disclosure provides an electrolytic capacitor that contains a liquid component and a conductive polymer layer and can reduce the ESR.
  • the manufacturing method according to this embodiment may be referred to as "manufacturing method (M)" below.
  • the manufacturing method (M) includes a preparation step, a polymer layer forming step (first polymer layer forming step), a laminate forming step, and a bonding step.
  • the polymer layer forming step, the laminate forming step, and the bonding step are performed in this order.
  • the preparation step is performed before the laminate forming step.
  • the preparation step may be performed before the polymer layer forming step.
  • the cathode foil having an inorganic layer on its surface may be prepared after the polymer layer forming step. Also, an impregnation step may be included after the bonding step.
  • an impregnation step may be included after the bonding step.
  • the preparation step is a step of preparing an anode foil having a dielectric layer on a surface thereof and a cathode foil having an inorganic layer on a surface thereof.
  • the inorganic layer is a layer containing at least one selected from the group consisting of carbon, titanium, and nickel, and may be a layer consisting of the at least one type.
  • the anode foil having a dielectric layer on its surface may be a commercially available product, or may be formed by forming a dielectric layer on the surface of a metal foil (anode foil).
  • the cathode foil having an inorganic layer on its surface may be a commercially available product, or may be formed by forming an inorganic layer on the surface of a metal foil (cathode foil).
  • the dielectric layer and the inorganic layer may be formed by a known method.
  • the dielectric layer may be formed by oxidizing the surface of the metal foil (anode foil).
  • the inorganic layer may be formed by a vacuum deposition method or the like.
  • the inorganic layer may be formed by applying a paste containing one selected from the group consisting of carbon (particularly a conductive carbon material), titanium, and nickel onto the metal foil (cathode foil) and then drying it.
  • the amount of the inorganic layer may be in the range of 50 mg/m 2 to 300 mg/m 2 (for example, in the range of 70 mg/m 2 to 200 mg/m 2 ).
  • the conductive carbon material contained in the inorganic layer include graphite, hard carbon, soft carbon, carbon black, and the like.
  • the inorganic layer may be a layer formed by vapor deposition of titanium, or may be a layer formed using titanium oxide particles.
  • the inorganic layer may be a layer formed by vapor deposition of nickel.
  • the inorganic layer may be a carbon layer.
  • the carbon layer may be a layer containing carbon, and may have a carbon content of 50 mass % or more. In this specification, the term "inorganic layer" may be replaced with "carbon layer”.
  • the cathode foil may include a metal foil, an inorganic layer, and a titanium-containing layer disposed between the inorganic layer and the metal foil.
  • An example of the cathode foil has a laminated structure of inorganic layer/titanium-containing layer/metal foil (e.g., aluminum foil)/titanium-containing layer/inorganic layer.
  • the titanium-containing layer may contain at least one selected from the group consisting of titanium and titanium compounds. Examples of titanium compounds include titanium nitride, titanium oxide, titanium aluminum alloy, titanium carbonate, and the like.
  • the method of forming the titanium-containing layer is not limited, and the layer may be formed by a known method.
  • the titanium-containing layer may be formed by a physical vapor deposition method such as a vacuum deposition method or a sputtering method.
  • the deposition amount of the titanium-containing layer may be in the range of 200 mg/m 2 to 500 mg/m 2 (e.g., in the range of 250 mg/m 2 to 400 mg/m 2 ).
  • the polymer layer forming step includes a first polymer layer forming step of forming a first conductive polymer layer in the voids of the separator.
  • the polymer layer forming step may further include a second polymer layer forming step of forming a second conductive polymer layer on the surface of the dielectric layer (the dielectric layer formed on the surface of the anode foil).
  • the first polymer layer forming step and the second polymer layer forming step may be performed in either order, or may be performed simultaneously.
  • the first polymer layer forming process includes a first coating liquid applying process of applying a first coating liquid containing a first conductive polymer and a first liquid medium into the voids of the separator, and a first liquid medium removing process of forming a first conductive polymer layer in the voids of the separator by removing at least a part of the first liquid medium from the first coating liquid.
  • the second polymer layer forming process includes a second coating liquid applying process of applying a second coating liquid containing a second conductive polymer and a second liquid medium onto the surface of the dielectric layer (the dielectric layer formed on the surface of the anode foil), and a second liquid medium removing process of forming a second conductive polymer layer on the surface of the dielectric layer by removing at least a part of the second liquid medium from the second coating liquid.
  • the second conductive polymer layer is usually formed on both sides of the anode foil.
  • the first conductive polymer and the second conductive polymer may be the same or different.
  • the first conductive polymer and the second conductive polymer may each be contained in the coating liquid in the form of particles. Examples of conductive polymers will be described later.
  • the liquid medium is not particularly limited, and any liquid medium that can be used to form a polymer layer can be used.
  • liquid media include water, organic solvents (e.g., alcohol), and mixed solvents thereof.
  • the first coating liquid and/or the second coating liquid may be a dispersion liquid in which conductive polymer particles are dispersed in water.
  • the first liquid medium and/or the second liquid medium may contain water and an organic compound that does not boil at 100°C at 1 atmosphere (101,325 Pa).
  • organic compound may be referred to as "organic compound (C).”
  • Organic compound (C) may be one type of compound or may be composed of multiple types of compounds.
  • the method of applying the coating liquid is not limited, and 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 coating liquid is first applied to a transfer member (such as a gravure roll), and excess coating liquid is removed from the transfer member.
  • the coating liquid applied to the transfer member is transferred to a specified member (anode foil, cathode foil, or separator), so that a layer of the coating liquid with a uniform thickness can be applied to the member.
  • 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 the inside of the separator, and a conductive polymer layer can be formed over the entire thickness of the separator.
  • the viscosity of the coating liquid may be, for example, 10 mPa ⁇ s or more (for example, 100 mPa ⁇ s or more) and 200 mPa ⁇ s or less.
  • the coating liquid can be easily applied to the anode foil, cathode foil, and separator, and can easily be impregnated into the separator.
  • the viscosity of the coating liquid is measured at room temperature (20°C) using a vibration viscometer (for example, VM-100A, manufactured by Sekonic Corporation).
  • the method of removing at least a part of the liquid medium from the coating liquid is not particularly limited, and can be performed by heating or the like.
  • heating may be performed so that the organic compound (C) remains in the polymer layer.
  • the coating liquid contains an organic compound (C) and water (liquid medium)
  • 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. There is no particular limit to the heating time, and it may be a time that allows a part of the liquid medium to be appropriately removed. An example of the heating time is in the range of 5 to 60 minutes.
  • the water content in the coating liquid is 40 mass % or more (e.g., 50 mass % or more), and the liquid medium of the applied coating liquid is removed so that the mass of the organic compound (C) in the conductive polymer layer is greater than the mass of water in the conductive polymer layer. If the water content in the coating liquid is high, the conductive polymer layer is more easily impregnated with the electrolyte after the conductive polymer layer is formed.
  • the first polymer layer formation step of manufacturing method (M) it is preferable to form the first conductive polymer layer so that the ratio of the area of the first conductive polymer layer to the surface of the separator (hereinafter, sometimes referred to as "ratio R") is 80% or more.
  • ratio R the ratio of the area of the first conductive polymer layer to the surface of the separator
  • the ratio R is the ratio of the area of the first conductive polymer layer occupying the surface of the separator to the area of the separator calculated from the size of the separator.
  • the ratio R can be calculated by acquiring an image of the surface of the separator on which the first conductive polymer layer is formed, and processing the image. Since the color of the first conductive polymer layer is usually different from the color of the separator, the area of the region on which the first conductive polymer layer is formed can be calculated by binarizing the image of the surface of the separator on which the first conductive polymer layer is formed.
  • the ratio R can then be calculated from the area Sp of the region on which the first conductive polymer layer is formed and the area Ss of the separator.
  • the ratio R can be calculated using the following formula.
  • Ratio R (%) (Sp/Ss) x 100
  • the surface density of the first conductive polymer layer may be 0.05 mg/cm2 or more , 0.1 mg/ cm2 or more, or 0.3 mg/cm2 or more , and may be 5.0 mg/cm2 or less , 1.0 mg/cm2 or less, or 0.5 mg/ cm2 or less.
  • the surface density of the first conductive polymer layer may be 0.05 mg/cm2 or more and 1.0 mg/cm2 or less . With this configuration, an electrolytic capacitor with a particularly low ESR is obtained.
  • the surface density means the mass per unit area.
  • the areal density of the second conductive polymer layer may be 0.05 mg/cm2 or more , 0.1 mg/ cm2 or more, or 0.3 mg/cm2 or more , and may be 5.0 mg/cm2 or less , 1.0 mg/cm2 or less, or 0.5 mg/ cm2 or less.
  • the areal density of the second conductive polymer layer means the areal density of one second conductive polymer layer formed on one side of the anode foil.
  • the areal density of the first conductive polymer layer can be determined by the following method. First, five samples are prepared by cutting out a specified area from the separator before the first conductive polymer layer is formed, and the mass of the five samples is measured. In addition, five samples are prepared by cutting out the separator on which the first conductive polymer layer is formed, and the mass of the samples is measured. The areal density of the first conductive polymer layer is determined using the specified area and the difference between the total mass of the five samples after the first conductive polymer layer is formed and the total mass of the five samples before the first conductive polymer layer is formed.
  • the ratio R can be changed by adjusting the viscosity of the coating liquid when applying the coating liquid containing the conductive polymer with a coater or the like.
  • the surface density of the conductive polymer layer can be controlled by the viscosity of the coating liquid.
  • the surface density of the conductive polymer may be controlled by the concentration of the conductive polymer in the coating liquid or the amount applied.
  • the viscosity of the coating liquid can be controlled by a condensation method or by using a thickener.
  • the laminate formation step is a step of forming a laminate including an anode foil, a cathode foil, and a separator disposed between the anode foil and the cathode foil.
  • the laminate formation step may be a step of forming a laminate including a first conductive polymer layer and a second conductive polymer layer by laminating the anode foil, the cathode foil, and the separator such that the separator is disposed between the anode foil and the cathode foil and the first conductive polymer layer faces the inorganic layer.
  • 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 disposed between the anode foil and the cathode foil.
  • the anode foil, the cathode foil, and the separator are stacked in the radial direction of the wound body.
  • the laminate may be formed by stacking flat anode foils, flat cathode foils, and flat separators in one direction.
  • a laminate may be formed by stacking multiple anode foils, multiple cathode foils, and multiple separators in one direction.
  • the anode foils and cathode foils are arranged alternately, and the separator is arranged between the anode foils and the cathode foils.
  • the adhesion step is a step of impregnating the laminate with a liquid containing an organic solvent (hereinafter, sometimes referred to as "liquid (L)”), thereby adhering the first conductive polymer layer to the inorganic layer. At least a part of the liquid (L) impregnated into the laminate is removed from the laminate after the adhesion step.
  • the method for removing the liquid (L) is not limited, and heating or the like may be used.
  • the adhesion between the first conductive polymer layer formed on the separator and the second conductive polymer layer formed on the dielectric layer is also improved.
  • the cathode foil is made of only a metal foil (e.g., aluminum foil)
  • a metal foil e.g., aluminum foil
  • an oxide layer is formed on the surface of the metal foil, and capacitance is also generated in the cathode foil.
  • the capacitance of the anode foil and the capacitance of the cathode foil are combined to create a problem that the capacitance of the entire capacitor decreases.
  • an inorganic layer etc.
  • the inorganic layer easily repels water
  • the conductive polymer is difficult to enter between the inorganic layer of the cathode foil and the anode foil in the laminate, so that the conductive polymer layer cannot be formed uniformly on the separator placed between the cathode foil and the anode foil, resulting in an increase in ESR.
  • a laminate is formed using a separator on which a first conductive polymer layer has been formed in advance.
  • the conductive polymer adheres to the inorganic layer without being repelled by the inorganic layer.
  • L liquid containing an organic solvent
  • the conductive polymer becomes entangled with the carbon. Therefore, the first conductive polymer layer and the inorganic layer can be firmly bonded, and the resistance between them can be reduced. As a result, an electrolytic capacitor with a low ESR can be manufactured.
  • the liquid (L) may be a liquid containing the organic compound (C) described above and water. In this case, it is preferable to impregnate the laminate with the liquid (L) and then remove the water from the laminate under conditions in which the organic compound (C) remains in the laminate.
  • the organic compound (C) may be at least one selected from the group consisting of xylitol and xylitol derivatives.
  • the liquid (L) may contain at least one selected from the group consisting of sugar, sugar alcohol, epoxy resin, and polyvinyl alcohol (hereinafter, sometimes referred to as "substance X").
  • substance X polyvinyl alcohol
  • the content of substance X in the liquid (L) may be in the range of 10% by mass to 70% by mass (for example, in the range of 30% by mass to 50% by mass).
  • the sugar alcohol may include at least one selected from the group consisting of mannitol, mannitol derivatives, xylitol, and xylitol derivatives, or may be at least one of the above.
  • the substance X may be at least one selected from the group consisting of mannitol, mannitol derivatives, xylitol, and xylitol derivatives. Mannitol, mannitol derivatives, xylitol, and xylitol derivatives have the effect of adhering the conductive polymer layer and the inorganic layer of the cathode foil.
  • Examples of xylitol derivatives include compounds in which some of the hydroxyl groups of xylitol are esterified, compounds in which some of the hydroxyl groups of xylitol are etherified, and compounds in which some of the hydroxyl groups of xylitol are anionized to form a salt.
  • Examples of mannitol derivatives include compounds in which some of the hydroxyl groups of mannitol are esterified, compounds in which some of the hydroxyl groups of mannitol are etherified, and compounds in which some of the hydroxyl groups of mannitol are anionized to form a salt.
  • the organic solvent contained in the liquid (L) may contain at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, or may be at least one of the organic solvents. By containing these in the liquid (L), the electrical conductivity of the conductive polymer layer can be increased.
  • a preferred example of the liquid (L) is a liquid containing xylitol in at least one organic solvent selected from the group consisting of triethylene glycol and polyethylene glycol.
  • the manufacturing method (M) may include an impregnation step after the adhesion step.
  • the impregnation step is a step of impregnating the laminate with a liquid component.
  • the liquid component may be referred to as a "liquid component (LC)" below.
  • the method of impregnating the laminate with the liquid component (LC) is not limited.
  • the laminate may be impregnated with the liquid component (LC) by immersing at least a part of the laminate in the liquid component (LC).
  • the liquid component (LC) may be an electrolyte solution.
  • the liquid component (LC) may contain at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol condensates having a molecular weight of 250 or less, glycerin, ⁇ -butyrolactone, and sulfolane. By including these compounds in the liquid component (LC), the withstand voltage of the capacitor can be increased.
  • a capacitor element e.g., a capacitor element impregnated with a liquid component (LC)
  • LC liquid component
  • the adhesion step and the impregnation step may be carried out simultaneously.
  • the liquid (L) is added to the liquid component (LC) to impregnate the laminate, and a part of the liquid (L) is then removed.
  • electrolytic capacitor The electrolytic capacitor according to this embodiment may be referred to as "electrolytic capacitor (E)" below.
  • the electrolytic capacitor (E) may be manufactured by the manufacturing method (M) described above.
  • the matters described for the manufacturing method (M) may be applied to the electrolytic capacitor (E), and therefore, duplicated explanations may be omitted.
  • the matters described for the electrolytic capacitor (E) may also be applied to the manufacturing method (M).
  • the electrolytic capacitor (E) includes a laminate and a liquid component (liquid component (LC)) impregnated in the laminate.
  • the laminate includes an anode foil having a dielectric layer on its surface, a cathode foil having an inorganic layer on its surface, a separator, a first conductive polymer layer held by the separator, and a second conductive polymer layer formed on the dielectric layer.
  • the first conductive polymer layer contains a first conductive polymer.
  • the second conductive polymer layer contains a second conductive polymer.
  • the ratio R of the area of the first conductive polymer layer to the area of the surface of the separator is 80% or more.
  • the first conductive polymer layer held by the separator is in close contact with the inorganic layer.
  • the electrolytic capacitor (E) provides the effects described in the manufacturing method (M).
  • the configuration of the electrolytic capacitor (E) makes it possible to reduce the ESR.
  • the areal density of the first conductive polymer layer may be in the range described above.
  • the areal density of the first conductive polymer layer may be 0.05 mg/cm2 or more and 1.0 mg/ cm2 or less.
  • the first conductive polymer layer may contain at least one selected from the group consisting of sugar, sugar alcohol, epoxy resin, and polyvinyl alcohol.
  • the sugar alcohol may include at least one selected from the group consisting of xylitol and xylitol derivatives.
  • the cathode foil may include a metal foil, an inorganic layer, and a titanium-containing layer disposed between the inorganic layer and the metal foil.
  • the titanium-containing layer may contain at least one selected from the group consisting of titanium and titanium compounds.
  • the laminate may be a wound body, or it may be a laminate other than a wound body.
  • the peel strength between the cathode foil and the separator may be 0.5 N/cm or more, or 1.0 N/cm or more. There is no particular upper limit to the peel strength.
  • the peel strength can be measured by the method described in the examples.
  • the peel strength between the cathode foil and the separator can be increased by performing an adhesion process.
  • the term "conductive polymer component" may be used.
  • the conductive polymer component is made of a conductive polymer.
  • the conductive polymer component is made of a conductive polymer and a dopant.
  • the coating liquid used in the polymer layer forming step may contain a conductive polymer and water.
  • the conductive polymer (conductive polymer component) may be contained in the coating liquid in the form of particles.
  • the coating liquid may be an aqueous dispersion of a conductive polymer (conductive polymer component).
  • the coating liquid may contain other components (for example, an organic compound (C)).
  • the organic compound (C) may contain at least one selected from the group consisting of polyhydric alcohols, sulfolane, ⁇ -butyrolactone, and boric acid esters, or may be at least one of the organic compounds.
  • the organic compound (C) may contain at least one selected from the group consisting of glycols, glycerins, sugar alcohols, sulfolane, ⁇ -butyrolactone, and boric acid esters, or may be at least one of the organic compounds.
  • polyhydric alcohols examples include glycols, glycerins, and sugar alcohols.
  • glycols include ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols (e.g., 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, and pentaerythritol, and the like.
  • Examples of conductive polymers include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, and derivatives thereof.
  • the derivatives include polymers having polypyrrole, polythiophene, polyfuran, polyaniline, and polyacetylene as the basic skeleton.
  • a derivative of polythiophene includes poly(3,4-ethylenedioxythiophene).
  • These conductive polymers may be used alone or in combination.
  • the conductive polymer may also 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. From the viewpoint of suppressing dedoping from the conductive polymer, it is preferable to use a polymer dopant as the dopant.
  • polymer dopants include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly(2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, polyacrylic acid, and the like. These may be used alone or in combination of two or more. At least a portion of these may be added in the form of a salt.
  • a preferred example of a dopant is polystyrene sulfonic acid (PSS).
  • the dopant may be polystyrenesulfonic 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 in order to suppress dedoping of the dopant, and may be 6.0 or less or 5.0 or less.
  • the pH of the coating liquid may be 1.0 or more, or 2.0 or more.
  • the water content in the coating liquid may be 40% by mass or more, 50% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more.
  • the water 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 of the organic compound (C) in the coating liquid may be 1.0 mass% or more, 3.0 mass% or more, 5.0 mass% or more, or 10 mass% or more. It may be 30 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less.
  • the content of the conductive polymer component in the coating liquid may be 0.5 mass% or more, or 1.0 mass% or more, and may be 4.0 mass% or less, 3.0 mass% or less, or 2.0 mass% or less.
  • the content may be in the range of 0.5 to 4.0 mass% or 1.0 to 4.0 mass%. In any of these ranges, the upper limit may be 3.0 mass% or 2.0 mass%.
  • the content is preferably in the range of 1.0 to 3.0%.
  • the mass of the dopant is included in the mass of the conductive polymer component.
  • the content of the conductive polymer component in the coating liquid may be 0.5 mass% or more, or 1.0 mass% or more, and may be 4.0 mass% or less, 3.0 mass% or less, or 2.0 mass% or less.
  • 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 there are no particular limitations on the mass of the dopant contained in the coating liquid, and it may be in the range of 0.1 to 5 times (e.g., 0.5 to 3 times) the mass of the conductive polymer contained in the coating liquid.
  • the water content: organic compound (C) content: conductive polymer component content may be 40-98:1.0-59.5:0.5-4.0, or the water content: organic compound (C) content: conductive polymer component content may be 69.5-98:1.0-30:0.5-4.0.
  • liquid component (LC) examples of the liquid component (LC) used in the impregnation step include a non-aqueous solvent and an electrolytic solution.
  • the electrolytic solution may be an electrolytic solution containing a non-aqueous solvent and a solute dissolved in the non-aqueous solvent.
  • the liquid component (LC) may be a component that is liquid at room temperature (25° C.) or a component that is liquid at the temperature when the electrolytic capacitor is used.
  • the non-aqueous solvent used in the liquid component (LC) 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), amides such as N-methylacetamide, N,N-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.
  • polyhydric alcohols such as ethylene glycol and propylene glycol
  • cyclic sulfones such as sulfolane (SL)
  • lactones such as ⁇ -butyrolactone ( ⁇ BL)
  • a polymer solvent may be used as the non-aqueous solvent.
  • polymer solvents include polyalkylene glycol, derivatives of polyalkylene glycol, and compounds in which at least one hydroxyl group in a polyhydric alcohol is replaced with polyalkylene glycol (including derivatives).
  • examples of polymer solvents 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, and polybutylene glycol.
  • polymer solvents further include ethylene glycol-propylene glycol copolymers, ethylene glycol-butylene glycol copolymers, and propylene glycol-butylene glycol copolymers.
  • the non-aqueous solvent may be used alone or in a mixture of two or more.
  • the liquid component (LC) may include a non-aqueous solvent and a base component (base) dissolved in the non-aqueous solvent.
  • the liquid component (LC) may also include 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.
  • the 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, itaconic acid), aromatic polycarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid), and alicyclic polycarboxylic acids (cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, etc.).
  • saturated polycarboxylic acids such as ox
  • Examples of the monocarboxylic acids include aliphatic monocarboxylic acids (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 (such as benzoic acid, cinnamic acid, naphthoic acid), and oxycarboxylic acids (such as salicylic acid, mandelic acid, resorcylic acid).
  • saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid
  • maleic acid, phthalic acid, benzoic acid, pyromellitic acid, and resorcylic acid are thermally stable and are preferably used.
  • Inorganic acids may be used as the acid component.
  • inorganic acids include phosphoric acid, phosphorous acid, hypophosphorous acid, alkyl phosphate esters, boric acid, boric fluoride, tetrafluoroboric acid, hexafluorophosphoric acid, benzenesulfonic acid, and naphthalenesulfonic acid.
  • composite compounds of organic acids and inorganic acids may be used as the acid component. Examples of such composite compounds include borodiglycolic acid, borodioxalic acid, and borodisalicylic acid.
  • 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-heptyl imidazoline, 1-methyl-2-(3'heptyl)imidazoline, 1-methyl-2-dodecyl imidazoline, 1,2-di
  • the base component may be a quaternary salt of a compound having an alkyl-substituted amidine group.
  • base components include imidazole compounds, benzimidazole compounds, and alicyclic amidine compounds (pyrimidine compounds, imidazoline compounds) that are quaternized with an alkyl group or arylalkyl group having 1 to 11 carbon atoms.
  • a tertiary amine may be used as the base component.
  • tertiary amines include trialkylamines (trimethylamine, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, dimethylisopropylamine, methylethyl-n-propylamine, methylethylisopropylamine, diethyl-n-propylamine, diethylisopropylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, etc.), and phenyl group-containing amines (dimethylphenylamine, methylethylphenylamine, diethylphenylamine, etc.).
  • trialkylamines are preferred in terms of increasing electrical conductivity, and it is more preferred 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 as the base component.
  • the liquid component (LC) may contain a salt of an acid component and a base component.
  • the salt may be an inorganic salt and/or an organic salt.
  • An organic salt is a salt in which at least one of the anion and the cation contains an organic substance. Examples of organic salts that may be used include trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono 1,2,3,4-tetramethylimidazolinium phthalate, and mono 1,3-dimethyl-2-ethylimidazolinium phthalate.
  • the pH of the liquid component (LC) may be less than 7.0 or less than 5.0, or may be greater than 1.0, or greater than 2.0.
  • the pH may be greater than 1.0 and less than 7.0 (e.g., in the range of 2.0 to 5.0).
  • the liquid component (LC) preferably contains a protic solvent. By using a protic solvent, it is possible to particularly swell the conductive polymer layer. In addition to the protic solvent, the liquid component (LC) may contain a solvent other than the protic solvent.
  • the protic solvent may include at least one selected from the group consisting of glycols, glycerin, polyglycerin, and sugar alcohols, or may be at least one of the above.
  • the protic solvent may be composed of only one type of compound, or may include multiple types of compounds.
  • the organic compound (C) and the liquid component (LC) may contain the same compound.
  • they may contain the same polyhydric alcohol, the same glycols (such as ethylene glycol), or the same sugar alcohol.
  • anode foil examples include metal foils containing at least one of valve metals such as titanium, tantalum, aluminum, and niobium, and may be metal foils of valve metals (e.g., aluminum foils).
  • 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 subjecting the anode foil to a chemical conversion treatment.
  • the dielectric layer may contain an oxide of a valve metal (e.g., aluminum oxide).
  • the dielectric layer may be formed of any dielectric other than an oxide of a valve metal as long as it functions as a dielectric.
  • a conductive polymer layer does not need to be formed on the end surface of the anode foil.
  • a dielectric layer is formed on the end surface of the anode foil.
  • the cathode foil includes a metal foil (e.g., aluminum foil).
  • the metal constituting the metal foil may be a valve metal or an alloy containing a valve metal.
  • the surface of the metal foil may be roughened by etching or the like.
  • the thickness of the cathode foil may be 15 ⁇ m or more and 300 ⁇ m or less.
  • the cathode foil includes a coating layer on its surface.
  • the coating layer is usually formed on both sides of the cathode foil.
  • the coating layer includes at least an inorganic layer disposed on its outermost surface.
  • the coating layer may consist of only an inorganic layer, or may include an inorganic layer and another layer (e.g., a titanium-containing layer).
  • a porous sheet can be used for the separator.
  • the porous sheet include woven fabric, nonwoven fabric, and microporous membrane.
  • the thickness of the separator is not particularly limited and may be in the range of 10 to 300 ⁇ m.
  • the material of the separator include cellulose, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, vinylon, nylon, aromatic polyamide, polyimide, polyamideimide, polyetherimide, rayon, glass, and the like.
  • the laminate and the liquid component (LC) are housed in an exterior body.
  • the exterior body includes a case and/or a sealing resin.
  • the sealing resin may include a thermosetting resin.
  • the thermosetting resin include an epoxy resin, a phenolic resin, a silicone resin, a melamine resin, a urea resin, an alkyd resin, a polyurethane, a polyimide, an unsaturated polyester, and the like.
  • the sealing resin may include a filler, a curing agent, a polymerization initiator, and/or a catalyst, and the like.
  • FIG. 1 is a cross-sectional view showing an example of an electrolytic capacitor 100 according to this embodiment.
  • FIG. 2 is a schematic diagram showing an exploded view of a portion of a capacitor element 10 included in the electrolytic capacitor 100.
  • the electrolytic capacitor 100 comprises a capacitor element 10, a bottomed case 101 that houses the capacitor element 10, a sealing member 102 that closes the opening of the bottomed case 101, a seat plate 103 that covers the sealing member 102, lead wires 104A, 104B that extend from the sealing member 102 and pass through the seat plate 103, and lead tabs 105A, 105B that connect the lead wires to the electrodes of the capacitor element 10.
  • the area near 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.
  • Capacitor element 10 is, for example, a wound body as shown in FIG. 1.
  • the wound body includes an anode foil 11 connected to lead tab 105A, a cathode foil 12 connected to lead tab 105B, and a separator 13.
  • Capacitor element 10 (wound body) includes a conductive polymer layer (not shown).
  • the conductive polymer layer may include an organic compound (C).
  • Electrolytic capacitor 100 includes a liquid component (LC) (e.g., an electrolyte) impregnated in capacitor element 10.
  • LC liquid component
  • the capacitor element 10 is formed by winding a strip-shaped anode foil 11 and a strip-shaped cathode foil 12 with a separator 13 between them.
  • the outermost circumference of the wound body is fixed with a stop tape 14. Note that Figure 2 shows the wound body in a partially unfolded state before the outermost circumference is fixed.
  • An electrolytic capacitor may have at least one capacitor element, but may also have multiple capacitor elements.
  • the number of capacitor elements included in an electrolytic capacitor may be determined according to the application.
  • An electrolytic capacitor comprising a laminate and a liquid component impregnated in the laminate,
  • the laminate comprises: an anode foil having a dielectric layer on a surface thereof; A cathode foil having an inorganic layer on a surface thereof; A separator; a first conductive polymer layer supported by the separator; the first conductive polymer layer contains a first conductive polymer, a ratio of an area of the first conductive polymer layer to an area of a surface of the separator is 80% or more; the first conductive polymer layer held by the separator is in close contact with the inorganic layer.
  • a method for manufacturing an electrolytic capacitor comprising the steps of: A preparation step of preparing an anode foil having a dielectric layer on a surface thereof and a cathode foil having an inorganic layer on a surface thereof; a first polymer layer forming step of forming a first conductive polymer layer in the voids of the separator; a laminate formation step of forming a laminate including the anode foil, the cathode foil, and a separator disposed between the anode foil and the cathode foil; a bonding step of bonding the first conductive polymer layer to the inorganic layer by impregnating the laminate with a liquid containing an organic solvent;
  • the first polymer layer forming step includes: a first coating liquid applying step of applying a first coating liquid containing a first conductive polymer and a first liquid medium into the voids of the separator; a first liquid medium removing step of removing at least a portion of the first liquid medium from the first coating liquid to form the first
  • the method further includes an impregnation step of impregnating the laminate with a liquid component,
  • Capacitor A1 An electrolytic capacitor (capacitor A1) was produced by the following method.
  • a nonwoven fabric (thickness 50 ⁇ m) was prepared as a separator.
  • the nonwoven fabric used was made of polyester fiber, aramid fiber, and cellulose.
  • a dispersion liquid (commercial product) in which particles of polyethylenedioxythiophene (PEDOT) doped with polystyrene sulfonic acid (PSS) were dispersed in water was prepared.
  • the coating liquid was applied to one side (surface of the dielectric layer) of the anode foil using a gravure coater.
  • a drying process was performed to form a conductive polymer layer on one side (surface of the dielectric layer) of the anode foil.
  • the drying process was performed by heating the anode foil coated with the coating liquid at 125° C. for 5 minutes.
  • a conductive polymer layer was formed on the other side (surface of the dielectric layer) of the anode foil in the same manner.
  • a conductive polymer layer was formed on the separator by applying the coating liquid to the separator and then performing a drying process.
  • liquid (L) was prepared.
  • an aqueous solution containing polyethylene glycol was used.
  • the concentration of polyethylene glycol was 10 mass%.
  • the wound body was impregnated with liquid (L), and then the wound body was dried by heating. In this way, the carbon layer (cathode foil) and the first conductive polymer layer were adhered to each other, and the first conductive polymer layer and the second conductive polymer layer were adhered to each other.
  • Capacitor C1 An electrolytic capacitor (capacitor C1) was produced in the same manner and under the same conditions as those for producing capacitor A1, except that the adhesion step was not performed.
  • ESR equivalent series resistance
  • laminate 11A laminate of anode foil and separator
  • portion of cathode foil 12A from which laminate 11A was peeled off were each set in a peel strength measuring device.
  • the measuring device used was an embossed tape high-speed peel strength tester (PTS-5000K) manufactured by EPI Co., Ltd.
  • the schematic configuration of an example of a measuring device 20 used to measure the peel strength is shown in FIG. 3.
  • the measuring device is preferably designed to perform a test conforming to JIS (Japanese Industrial Standards) C0806-3:2014.
  • the measuring device 20 includes a feed sheet 21, a feed roller 22, and a recovery device 23.
  • the outer peripheral surface of the peeled laminate 11A is fixed to the feed sheet 21 by a fixing jig 24.
  • the feed sheet 21 is fed in a first direction by the feed roller 22.
  • the recovery device 23 recovers the above-mentioned portion 12A of the cathode foil 12 while pulling it in a second direction opposite to the first direction.
  • the recovery device 23 has a winding roller that winds up the cathode foil 12.
  • the feed speed of the laminate 11A (anode foil 11 and separator 13) by the feed roller 22 and the winding speed of the cathode foil 12 by the recovery device 23 are controlled so that the position of the capacitor element 10 does not move during measurement
  • the laminate 11A and the cathode foil 12 were pulled so that the angle between the direction in which the laminate 11A (anode foil 11 and separator 13) fixed to the feed sheet 21 was pulled in the measuring device 20 and the direction in which the cathode foil 12 was pulled by the recovery device 23 was approximately 175°.
  • the laminate 11A and the cathode foil 12 were pulled for 60 seconds so that the cathode foil 12 and the separator 13 were continuously peeled off at a constant speed (160 mm/min).
  • the force pulling the cathode foil 12 at this time was measured at sampling intervals of 0.01 seconds.
  • the average value of the measured forces pulling the cathode foil 12 was taken as the peel strength.
  • the captured image was binarized using image analysis software (Adobe Photoshop (registered trademark)). At this time, binarization was performed so that the image of the separator alone was used as a reference and the area where the conductive polymer was attached was recognized as black. From the binarized image, the proportion R of capacitor A1 and the proportion R of capacitor C1 were calculated.
  • Capacitor A1 is an electrolytic capacitor (E) according to the present disclosure manufactured by manufacturing method (M).
  • Capacitor C1 is a comparative example. As shown in Table 1, capacitor A1, which has a high ratio R, had a high peel strength between the cathode foil and the separator and a low ESR.
  • This disclosure can be used in electrolytic capacitors.
  • Capacitor element 11 Anode foil 12: Cathode foil 13: Separator 14: Stop tape 100: Electrolytic capacitor 101: Bottomed case 102: Sealing member 103: Seat plate 104A, 104B: Lead wires 105A, 105B: Lead tabs

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US20250095923A1 (en) * 2022-01-28 2025-03-20 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor and method for manufacturing electrolytic capacitor

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WO2020158780A1 (ja) * 2019-01-31 2020-08-06 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その製造方法
WO2021261359A1 (ja) * 2020-06-22 2021-12-30 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ素子および固体電解コンデンサ
JP2022117355A (ja) * 2021-01-29 2022-08-10 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その製造方法

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WO2020158780A1 (ja) * 2019-01-31 2020-08-06 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その製造方法
WO2021261359A1 (ja) * 2020-06-22 2021-12-30 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ素子および固体電解コンデンサ
JP2022117355A (ja) * 2021-01-29 2022-08-10 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その製造方法

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US20250095923A1 (en) * 2022-01-28 2025-03-20 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor and method for manufacturing electrolytic capacitor

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