WO2023120309A1 - Procédé de production d'un condensateur électrolytique - Google Patents

Procédé de production d'un condensateur électrolytique Download PDF

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Publication number
WO2023120309A1
WO2023120309A1 PCT/JP2022/045965 JP2022045965W WO2023120309A1 WO 2023120309 A1 WO2023120309 A1 WO 2023120309A1 JP 2022045965 W JP2022045965 W JP 2022045965W WO 2023120309 A1 WO2023120309 A1 WO 2023120309A1
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conductive polymer
layer
anode body
anode
polymer layer
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PCT/JP2022/045965
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English (en)
Japanese (ja)
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孝裕 小林
剛士 古川
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パナソニックＩｐマネジメント株式会社
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Publication of WO2023120309A1 publication Critical patent/WO2023120309A1/fr

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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
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • the present invention relates to a method for manufacturing an electrolytic capacitor.
  • Electrolytic capacitors have a low equivalent series resistance (ESR) and excellent frequency characteristics, so they are installed in various electronic devices. Electrolytic capacitors typically comprise a capacitor element comprising an anode portion and a cathode portion. The anode part includes a porous anode body, and a dielectric layer is formed on the surface of the anode body. The dielectric layer contacts the electrolyte. As an electrolyte, there is an electrolytic capacitor using a solid electrolyte such as a conductive polymer (see, for example, Patent Document 1).
  • Patent Document 2 discloses that (i) a first conductive polymer is added in the presence of a silane compound to the dielectric layer of the anode body on which the dielectric layer is formed. (ii) comprising a second conductive polymer and a basic compound on the first conductive polymer layer, and a first forming a second conductive polymer layer overlying at least a portion of the first conductive polymer layer.
  • the oxidizing agent and dopant used in polymerization easily combine with water, so a large amount of water remains in the polymer film. can.
  • the outer conductive polymer layer peels off due to vaporization and expansion of water, and the solid electrolyte layer tends to be poorly formed due to swelling.
  • one aspect of the present disclosure provides a porous anode body, a dielectric layer formed on the surface of the anode body, a solid electrolyte layer covering at least a portion of the dielectric layer, and the solid electrolyte and a cathode layer covering at least a part of the layer, the step of forming the solid electrolyte layer containing a conductive polymer on the surface of the anode body on which the dielectric layer is formed.
  • the step of forming the solid electrolyte layer includes impregnating the anode body with a first solution containing a first monomer that is a raw material of the first conductive polymer, and forming the first a first step of polymerizing one monomer to form a first conductive polymer layer covering the dielectric layer; a second step of impregnating and forming a second conductive polymer layer covering the first conductive polymer layer, wherein the second step includes subjecting the anode body to a reduced pressure treatment;
  • the present invention relates to a method for manufacturing an electrolytic capacitor.
  • an electrolytic capacitor comprising a solid electrolyte layer formed of a plurality of conductive polymer layers, it is possible to improve the adhesion between the conductive polymer layers, so that swelling of the conductive polymer layer due to vaporization expansion of moisture etc. can be prevented. Defects due to are reduced.
  • FIG. 1 is a cross-sectional view schematically showing an example of a capacitor element of an electrolytic capacitor manufactured by a manufacturing method according to an embodiment of the present disclosure
  • FIG. 1 is a cross-sectional view schematically showing an electrolytic capacitor manufactured by a manufacturing method according to an embodiment of the present disclosure
  • FIG. 4 is a flow chart showing an example of a step of forming a fixed electrolyte layer in the method of manufacturing an electrolytic capacitor according to the present embodiment.
  • 4 is a flow chart showing another example of a step of forming a fixed electrolyte layer in the method of manufacturing an electrolytic capacitor according to the present embodiment.
  • the present disclosure encompasses a combination of matters described in two or more claims arbitrarily selected from the multiple claims described in the attached claims. In other words, as long as there is no technical contradiction, the items described in two or more claims arbitrarily selected from the multiple claims described in the attached claims can be combined.
  • a method for manufacturing an electrolytic capacitor according to an embodiment of the present disclosure includes a porous anode body, a dielectric layer formed on the surface of the anode body, a solid electrolyte layer covering at least a portion of the dielectric layer, a solid a cathode layer covering at least a portion of the electrolyte layer, the method comprising the step of forming a solid electrolyte layer containing a conductive polymer on the surface of an anode body having a dielectric layer formed thereon.
  • the anode body is impregnated with a first solution containing a first monomer as a raw material of the first conductive polymer, and the first monomer is polymerized on the surface of the dielectric layer to form a dielectric layer.
  • an oligomer is contained in a 1st monomer.
  • a dispersion of a conductive polymer includes a solution of a conductive polymer.
  • the second step includes depressurizing the anode body.
  • the depressurization treatment may be performed before drying the second dispersion impregnated in the anode body, and there are no particular limitations on the depressurization start time, treatment time and method.
  • the anode body may be immersed in the second dispersion under reduced pressure and released to atmospheric pressure to impregnate the second dispersion into the anode body, or the anode body may be impregnated with the second dispersion.
  • the second dispersion may be impregnated into the anode body by pulling up the body and decompressing and releasing the anode body with the second dispersion adhered thereon to the atmospheric pressure.
  • the depressurization process is started in a state in which the fluidity of the second conductive polymer in the second dispersion is sufficiently ensured.
  • the decompression treatment may be started when the content of the second conductive polymer in the second dispersion impregnated in the anode body is 90% by mass or less, 75% by mass or less, or 50% by mass or less.
  • the surface of the first conductive polymer layer (eg, chemically polymerized layer) formed by polymerization has fine irregularities when viewed microscopically.
  • the second conductive polymer can penetrate deep into the recesses on the surface of the first conductive polymer layer, and the second conductive polymer layer and the first conductive polymer layer can be separated. Adhesion can be improved.
  • the formation of voids in the concave portion that is the starting point of swelling is also suppressed. This suppresses the second conductive polymer layer from peeling off from the first conductive polymer layer and causing swelling.
  • the reduced pressure treatment can prevent swelling of the dispersion liquid containing the second conductive polymer (polymer dispersion), which tends to accumulate in the lower portion of the anode body, during drying, and suppress variation in characteristics due to insufficient adhesion.
  • the pressure during the decompression process should be at least lower than the atmospheric pressure.
  • the pressure during the decompression process may be, for example, a pressure lower than the atmospheric pressure by 50 kPa or more, or a pressure lower than the atmospheric pressure by 100 kPa or more.
  • the treatment time for reducing pressure may be 1 minute or more and 10 minutes or less, or may be 2 minutes or more and 10 minutes or less.
  • the anode body may be impregnated with a solution or solvent containing a basic compound before impregnating the anode body with the second dispersion.
  • the cation contained in the basic compound suppresses the repulsion of the anionic dopant contained in the conductive polymer, thereby increasing the adhesion between the second conductive polymer layer and the first conductive polymer layer.
  • the surface of the first conductive polymer layer is precoated with a basic compound layer, and the second conductive polymer layer is formed on the surface of the first conductive polymer layer precoated with the basic compound layer. This further improves the adhesion of the second conductive polymer layer to the first conductive polymer layer. This further suppresses the second conductive polymer layer from peeling off from the first conductive polymer layer and causing swelling.
  • a third solution or third dispersion containing a third conductive polymer (hereinafter, unless otherwise specified, “third solution or third dispersion liquid” is simply referred to as “third dispersion liquid”, and the description of the third solution is omitted.) is impregnated into the anode body to form a third conductive polymer layer. good too.
  • the anode body may be impregnated with a solution or solvent containing a basic compound before impregnating the anode body with the third dispersion.
  • the surface of the second conductive polymer layer is pre-coated with a basic compound layer, and the third conductive polymer layer is formed on the surface of the second conductive polymer layer pre-coated with the basic compound layer.
  • the adhesion of the third conductive polymer layer to the second conductive polymer layer is improved, and as a result, the third conductive polymer layer is peeled off from the second conductive polymer layer, causing swelling. is suppressed.
  • the second conductive polymer layer when forming the second conductive polymer layer on the first conductive polymer layer, if the surface of the first conductive polymer layer is pre-coated with a layer containing a basic compound, part of the basic compound dissolves into the second dispersion, increasing the viscosity of the second dispersion.
  • the recesses on the surface of the first conductive polymer layer are particularly fine compared to other conductive polymer layers formed thereon, and the recesses between the second conductive polymer layer and the first conductive polymer layer are particularly fine.
  • the surface of the first conductive polymer layer is pre-coated with a basic compound so that the second conductive polymer can easily penetrate deep into the recesses on the surface of the first conductive polymer layer.
  • the second conductive polymer layer may be formed directly on the first conductive polymer layer.
  • the second conductive polymer layer is directly formed without precoating the surface of the first conductive polymer layer with a basic compound. is preferred.
  • the anode body is not impregnated with a solution or solvent containing a basic compound in the second step.
  • the surface of the conductive polymer layer may not be precoated with a basic compound.
  • the solid electrolyte layer may be formed of two conductive polymer layers, or may be formed of three or more conductive polymer layers.
  • amine compounds or amidine compounds such as N,N-dimethyloctylamine and 1,8-diaminooctane can be preferably used.
  • a first conductive polymer contained in the first conductive polymer layer, a second conductive polymer contained in the second conductive polymer layer, and a third conductive polymer contained in the third conductive polymer layer may each contain the same or different monomeric units.
  • the third conductive polymer preferably contains the same monomer units as those constituting the second conductive polymer.
  • a thick conductive polymer layer having the same monomer skeleton can be formed.
  • FIG. 1 is a cross-sectional view schematically showing an example of a capacitor element of an electrolytic capacitor manufactured by the manufacturing method according to this embodiment.
  • FIG. 2 is a schematic cross-sectional view of an electrolytic capacitor manufactured by the manufacturing method according to this embodiment.
  • Electrolytic capacitor 20 is electrically connected to capacitor element 10 having anode portion 6 and cathode portion 7, exterior body 11 that seals capacitor element 10, and anode section 6, and a portion of exterior body 11 extends from An exposed anode lead terminal 13 and a cathode lead terminal 14 electrically connected to the cathode section 7 and partly exposed from the exterior body 11 are provided.
  • Anode section 6 has anode body 1 and anode wire 2 .
  • a dielectric layer 3 is formed on the surface of the anode body.
  • Cathode portion 7 has solid electrolyte layer 4 covering at least part of dielectric layer 3 and cathode layer 5 covering at least part of the surface of solid electrolyte layer 4 .
  • capacitor element 10 will be described in detail, taking as an example a case in which a solid electrolyte layer is provided as an electrolyte.
  • Anode section 6 has anode body 1 and anode wire 2 extending from one surface of anode body 1 and electrically connected to anode lead terminal 13 .
  • Anode body 1 is, for example, a cuboid porous sintered body obtained by sintering metal particles.
  • the metal particles particles of valve action metals such as titanium (Ti), tantalum (Ta) and niobium (Nb) are used.
  • One or two or more kinds of metal particles are used in anode body 1 .
  • the metal particles may be an alloy of two or more metals.
  • an alloy containing a valve action metal and silicon, vanadium, boron, or the like can be used.
  • a compound containing a valve action metal and a typical element such as nitrogen may also be used.
  • the alloy of the valve action metal is mainly composed of the valve action metal, and contains, for example, 50 atomic % or more of the valve action metal.
  • the anode wire 2 is made of a conductive material.
  • the material of the anode wire 2 is not particularly limited, and examples thereof include the above-described valve action metals, copper, aluminum, aluminum alloys, and the like.
  • the materials constituting anode body 1 and anode wire 2 may be of the same type or of different types.
  • Anode wire 2 has a first portion 2 a embedded inside anode body 1 from one surface of anode body 1 and a second portion 2 b extending from the one surface of anode body 1 .
  • the cross-sectional shape of the anode wire 2 is not particularly limited, and may be circular, track-shaped (a shape consisting of mutually parallel straight lines and two curved lines connecting the ends of these straight lines), elliptical, rectangular, polygonal, and the like. be done.
  • the anode portion 6 is produced, for example, by embedding the first portion 2a in the powder of the first metal particles, molding the first portion 2a into a rectangular parallelepiped shape, and sintering the first portion. As a result, the second portion 2b of the anode wire 2 is pulled out from one surface of the anode body 1 so as to be erected. The second portion 2b is joined to the anode lead terminal 13 by welding or the like, so that the anode wire 2 and the anode lead terminal 13 are electrically connected.
  • the welding method is not particularly limited, and includes resistance welding, laser welding, and the like.
  • a dielectric layer 3 is formed on the surface of the anode body 1 .
  • the dielectric layer 3 is made of metal oxide, for example.
  • a method for forming a layer containing a metal oxide on the surface of anode body 1 for example, anode body 1 is immersed in a chemical solution to anodize the surface of anode body 1, or anode body 1 is immersed in oxygen.
  • the dielectric layer 3 is not limited to the layer containing the above-mentioned metal oxide, and may have insulating properties.
  • the cathode section 7 has a solid electrolyte layer 4 and a cathode layer 5 covering the solid electrolyte layer 4 .
  • Solid electrolyte layer 4 is formed to cover at least a portion of dielectric layer 3 .
  • a manganese compound or a conductive polymer is used for the solid electrolyte layer 4 .
  • conductive polymers include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, and the like. These may be used alone, or may be used in combination. Also, the conductive polymer may be a copolymer of two or more monomers. Polythiophene, polyaniline, and polypyrrole may be used from the viewpoint of excellent conductivity. In particular, polypyrrole may be used because of its excellent water repellency.
  • the solid electrolyte layer 4 containing the conductive polymer is composed of two or more solid electrolyte layers, for example, a first conductive polymer layer covering the dielectric layer 3 and a first conductive polymer layer covering the first conductive polymer layer.
  • a second conductive polymer layer is included.
  • the composition and formation method (polymerization method) of the conductive polymer used for each layer may be different.
  • the first conductive polymer layer may be formed by polymerizing raw material monomers on the dielectric layer 3 .
  • the second conductive polymer layer may be formed by applying a liquid containing the conductive polymer to the dielectric layer 3 .
  • polypyrrole, polythiophene, polyfuran, polyaniline, etc. mean polymers having polypyrrole, polythiophene, polyfuran, polyaniline, etc. as a basic skeleton, respectively. Therefore, polypyrrole, polythiophene, polyfuran, polyaniline, etc. may also include their respective derivatives.
  • polythiophenes include poly(3,4-ethylenedioxythiophene) and the like.
  • dopants may be added to the polymerization liquid, solution or dispersion of the conductive polymer for forming the conductive polymer, in order to improve the conductivity of the conductive polymer.
  • the dopant is not particularly limited, examples include naphthalenesulfonic acid, p-toluenesulfonic acid, polystyrenesulfonic acid and the like.
  • the average particle diameter D50 of the particles is, for example, 0.01 ⁇ m or more and 0.5 ⁇ m or less. If the average particle diameter D50 of the particles is within this range, the particles can easily penetrate into the interior of anode body 1 .
  • the cathode layer 5 has, for example, a carbon layer 5a formed to cover the solid electrolyte layer 4 and a metal paste layer 5b formed on the surface of the carbon layer 5a.
  • the carbon layer 5a contains a conductive carbon material such as graphite and a resin.
  • the metal paste layer 5b contains, for example, metal particles (for example, silver) and resin.
  • the structure of the cathode layer 5 is not limited to this structure.
  • the configuration of the cathode layer 5 may be any configuration as long as it has a current collecting function.
  • a basic compound When the solid electrolyte layer 4 is composed of a plurality of conductive polymer layers, a basic compound may be interposed between the conductive polymer layers in order to improve adhesion between the conductive polymer layers.
  • Basic compounds include inorganic bases such as ammonia, as well as organic bases such as amine compounds.
  • amine compounds are preferable from the viewpoint of being highly effective in suppressing a decrease in conductivity. Any of a primary amine, a secondary amine, and a tertiary amine may be sufficient as an amine compound.
  • Amine compounds include aliphatic amines and cyclic amines.
  • a basic compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Aliphatic amines include alkylamines such as ethylamine, diethylamine, triethylamine, N,N-dimethyloctylamine and N,N-diethyloctylamine; alkanolamines such as ethanolamine, 2-ethylaminoethanol and diethanolamine; -ethylethylenediamine, alkylenediamine such as 1,8-diaminooctane, and the like.
  • Alicyclic amines include, for example, aminocyclohexane, diaminocyclohexane, and isophoronediamine. Examples of aromatic amines include aniline and toluidine.
  • Cyclic amines are preferably cyclic amines having a 5- to 8-membered (preferably 5- or 6-membered) nitrogen-containing ring skeleton, such as pyrrole, imidazoline, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, and triazine. Cyclic amines may have one nitrogen-containing ring skeleton, or two or more (eg, two or three). When the cyclic amine has more than one nitrogen-containing ring skeleton, the nitrogen-containing ring skeletons may be the same or different.
  • the amine compound may have a substituent as necessary. Whether the conductive polymer layer contains an amine compound can be analyzed, for example, by gas chromatography (GC).
  • GC gas chromatography
  • Anode lead terminal 13 is electrically connected to anode body 1 through second portion 2 b of anode wire 2 .
  • the material of anode lead terminal 13 is not particularly limited as long as it is electrochemically and chemically stable and has conductivity.
  • the anode lead terminal 13 may be made of metal such as copper, or may be made of non-metal.
  • the shape is not particularly limited as long as it is flat.
  • the thickness of anode lead terminal 13 (the distance between the main surfaces of anode lead terminal 13) may be 25 ⁇ m or more and 200 ⁇ m or less, and may be 25 ⁇ m or more and 100 ⁇ m or less, from the viewpoint of height reduction.
  • anode lead terminal 13 may be joined to the anode wire 2 with a conductive adhesive or solder, or may be joined to the anode wire 2 by resistance welding or laser welding.
  • the other end of anode lead terminal 13 is led out of package 11 and exposed from package 11 .
  • the conductive adhesive is, for example, a mixture of a thermosetting resin, which will be described later, and carbon particles or metal particles.
  • the cathode lead terminal 14 is electrically connected to the cathode portion 7 at the joint portion 14a.
  • the junction portion 14 a is a portion where the cathode lead terminal 14 overlaps the cathode layer 5 .
  • the cathode lead terminal 14 is joined to the cathode layer 5 via a conductive adhesive 8, for example.
  • One end of the cathode lead terminal 14 constitutes, for example, a part of the joint portion 14 a and is arranged inside the exterior body 11 .
  • the other end of the cathode lead terminal 14 is led out to the outside. Therefore, a portion including the other end of cathode lead terminal 14 is exposed from exterior body 11 .
  • the material of the cathode lead terminal 14 is also not particularly limited as long as it is electrochemically and chemically stable and has conductivity.
  • the cathode lead terminal 14 may be made of metal such as copper, or may be made of non-metal.
  • the shape is not particularly limited, either, and for example, it is long and flat.
  • the thickness of the cathode lead terminal 14 may be 25 ⁇ m or more and 200 ⁇ m or less, or may be 25 ⁇ m or more and 100 ⁇ m or less, from the viewpoint of height reduction.
  • the exterior body 11 is provided to electrically insulate the anode lead terminal 13 and the cathode lead terminal 14, and is made of an insulating material (sheath material).
  • the exterior body material includes, for example, thermosetting resin.
  • thermosetting resins include epoxy resins, phenol resins, silicone resins, melamine resins, urea resins, alkyd resins, polyurethanes, polyimides, unsaturated polyesters, and the like.
  • Capacitor Element Preparing Step First, a capacitor element is prepared.
  • the steps of preparing the capacitor element include, for example, preparing an anode body, covering at least part of the anode body with a dielectric layer, covering at least part of the dielectric layer with a solid electrolyte layer, and solid and covering at least a portion of the electrolyte layer with a carbon layer.
  • the step of preparing the capacitor element may further include the step of covering at least part of the carbon layer with a conductive resin layer.
  • anode body Preparing Step
  • a porous sintered body can be used as the anode body 1.
  • the valve-acting metal particles and the anode wire 2 are placed in a mold so that the first portion 2a is embedded in the valve-acting metal particles, pressure-molded, and then sintered to form an anode body, which is a porous body of the valve-acting metal.
  • An anode portion 6 containing 1 is obtained.
  • a first portion 2a of the anode wire is embedded inside the porous sintered body from one side thereof.
  • the pressure during pressure molding is not particularly limited. Sintering is preferably performed under reduced pressure.
  • the valve metal particles may be mixed with a binder such as polyacrylic carbonate.
  • valve action metal particles are usually pressure-molded and sintered using a mold with a rectangular parallelepiped internal space.
  • shape of anode body 1 after sintering is also a rectangular parallelepiped and has a plurality of main surfaces.
  • anode body 1 is subjected to chemical conversion treatment, and at least a portion of anode body 1 is covered with dielectric layer 3 .
  • the anode body 1 is immersed in an anodizing tank filled with an electrolytic aqueous solution (for example, a phosphoric acid aqueous solution), the second portion 2b of the anode wire 2 is connected to the anode body in the anodizing tank, and anodization is performed.
  • an electrolytic aqueous solution is not limited to the phosphoric acid aqueous solution, and nitric acid, acetic acid, sulfuric acid, or the like can be used.
  • Step of Forming Solid Electrolyte Layer Subsequently, at least part of the dielectric layer 3 is covered with the solid electrolyte layer 4 .
  • Capacitor element 10 including anode body 1 , dielectric layer 3 , and solid electrolyte layer 4 is thus obtained.
  • a solid electrolyte layer 4 including a plurality of conductive polymer layers may be formed.
  • the anode body is impregnated with a solution containing a first monomer as a raw material of the first conductive polymer, and the first monomer is polymerized on the surface of the dielectric layer to form the dielectric layer.
  • FIG. 3 is a flow chart showing an example of a step of forming a fixed electrolyte layer in the method of manufacturing an electrolytic capacitor according to this embodiment.
  • a first conductive polymer layer is formed on anode body 1 having dielectric layer 3 formed thereon by impregnating with a monomer or oligomer and then polymerizing the monomer or oligomer by chemical polymerization or electrolytic polymerization.
  • the first conductive polymer may contain a dopant.
  • the conductive polymer and dopant may be selected from those exemplified for the solid electrolyte layer 4, respectively.
  • the raw material monomer of the first conductive polymer is oxidatively polymerized (so-called “in situ polymerization”) above the dielectric layer 3 to form the dielectric layer 3.
  • a first conductive polymer layer is formed thereover.
  • the surface of the first conductive polymer layer may have fine unevenness due to non-uniform polymerization reaction, non-uniform layer growth, and the like.
  • step (ii) first, the anode body is impregnated with a solution or solvent containing a basic compound. After that, the solvent is removed by drying, and the basic compound is attached to the surface of the first conductive polymer layer.
  • a solvent is, for example, water.
  • the treatment of adhering the basic compound includes, prior to the formation of the second conductive polymer layer, the anionic first dopant doped into the first conductive polymer in the first conductive polymer layer and the first By suppressing electrostatic repulsion with the anionic second dopant doped into the second conductive polymer in the two conductive polymer layers, the first conductive polymer layer and the second conductive polymer layer This is done to increase the adhesion with. Therefore, the basic compound is precoated along the unevenness of the surface of the first conductive polymer layer.
  • the basic compound may be selected from the compounds already listed (eg, amine compounds).
  • the anode body 1 in which the first conductive polymer layer is precoated with a basic compound is immersed in a second dispersion containing a prepolymerized second conductive polymer, taken out, and decompressed. Dry after treatment or at the same time as vacuum treatment.
  • the second conductive polymer layer is formed on at least a portion of the first conductive polymer layer.
  • the dispersion may include a binder and/or conductive inorganic particles (eg, a conductive carbon material such as carbon black).
  • step (ii) is performed under reduced pressure. It is desirable that the decompression treatment be performed before the step of drying the anode body impregnated with the second dispersion. Thereby, the adhesion between the first conductive polymer layer and the second conductive polymer layer can be improved.
  • the anode body is immersed in the second dispersion liquid, pulled up from the solution or the dispersion liquid, and then the anode body to which the second dispersion liquid has adhered is subjected to reduced pressure treatment.
  • reduced pressure treatment good too.
  • Adhesion of the second conductive polymer layer to the first conductive polymer layer is not sufficient, and a gap is formed between the concave portion on the surface of the first conductive polymer layer and the second conductive polymer layer. Even in this case, the air present in the gaps is released by the reduced pressure, and the second conductive polymer layer having fluidity easily fills the gaps in the recesses of the first conductive polymer layer.
  • the recovered atmospheric pressure pushes the second conductive polymer layer toward the first conductive polymer layer, making it easier to fill the concave portions of the first conductive polymer layer.
  • the adhesion between the first conductive polymer layer and the second conductive polymer layer is improved.
  • the anode body may be impregnated with the second dispersion liquid under reduced pressure.
  • the solution or dispersion liquid can easily enter the recesses of the first conductive polymer layer. , the adhesion between the first conductive polymer layer and the second conductive polymer layer is improved.
  • FIG. 4 is a flow chart showing another example of the process of forming a fixed electrolyte layer in the method of manufacturing an electrolytic capacitor according to this embodiment.
  • the step of impregnating the anode body with a third dispersion containing the third conductive polymer to form the third conductive polymer layer ( iii) is performed.
  • step (iii) first, the anode body is impregnated with a solution or solvent containing a basic compound. After that, the solvent is removed by drying, and the basic compound is attached to the surface of the second conductive polymer layer.
  • a basic compound is pre-coated along the unevenness of the surface of the second conductive polymer layer.
  • a solvent is, for example, water.
  • the basic compound may be selected from the compounds already listed (eg, amine compounds). The basic compound can enhance the adhesion between the second conductive polymer layer and the third conductive polymer layer.
  • the anode body 1 is immersed in a third dispersion containing a prepolymerized third conductive polymer, taken out, and dried.
  • the third conductive polymer layer is formed on at least part of the second conductive polymer layer.
  • the dispersion may include a binder and/or conductive inorganic particles (eg, a conductive carbon material such as carbon black).
  • step (iii) may be performed under reduced pressure.
  • the decompression treatment is performed before the step of drying the anode body impregnated with the third dispersion.
  • the anode body to which the third dispersion is adhered may be subjected to reduced pressure treatment, or the anode body may be impregnated with the third dispersion under reduced pressure.
  • the basic compound When the basic compound is attached to the surface of the second conductive polymer layer in step (iii), the basic compound may not be attached to the surface of the first conductive polymer layer in step (ii).
  • a dopant may be contained in the second and third conductive polymers.
  • the conductive polymer and dopant may be selected from those exemplified for the solid electrolyte layer 4, respectively.
  • a known binder can be used.
  • the dispersion may contain known additives used in forming the solid electrolyte layer.
  • Step of forming a carbon layer and a conductive resin layer Subsequently, a carbon paste and a metal paste are sequentially applied to the surface of the solid electrolyte layer 4 to form a carbon layer 5a and a metal paste layer 5b.
  • a cathode layer 5 is formed.
  • the configuration of the cathode layer 5 is not limited to this, as long as it has a current collecting function.
  • anode lead terminal 13 and cathode lead terminal 14 are prepared.
  • a second portion 2b of anode wire 2 erected from anode body 1 is joined to anode lead terminal 13 by laser welding, resistance welding, or the like.
  • the conductive adhesive 8 is applied to the cathode layer 5
  • the cathode lead terminal 14 is joined to the cathode portion 7 via the conductive adhesive 8 .
  • capacitor element 10 and exterior body 11 for example, uncured thermosetting resin and filler
  • materials of capacitor element 10 and exterior body 11 for example, uncured thermosetting resin and filler
  • capacitor element 10 is sealed by transfer molding, compression molding, or the like.
  • the anode lead terminal 13 and the cathode lead terminal 14 are partly exposed from the mold.
  • the molding conditions are not particularly limited, and the time and temperature conditions may be appropriately set in consideration of the curing temperature of the thermosetting resin used.
  • anode lead terminal 13 and cathode lead terminal 14 are bent along exterior body 11 to form bent portions.
  • a part of anode lead terminal 13 and cathode lead terminal 14 is arranged on the mounting surface of package 11 .
  • the electrolytic capacitor 20 is manufactured by the above method.
  • An electrolytic capacitor was produced in the following manner.
  • Tantalum metal particles were used as the valve action metal.
  • the tantalum metal particles were formed into a rectangular parallelepiped so that one end of the anode wire made of tantalum metal was embedded in the tantalum metal particles, and then the compact was sintered in vacuum.
  • an anode body (1.7 mm ⁇ 3.3 mm ⁇ 4.4 mm) made of a porous sintered body of tantalum and an anode having one end embedded in the anode body and the remaining portion planted from one surface of the anode body An anode part containing a wire was obtained.
  • the anode body and part of the anode wire planted from the anode body were immersed in a chemical bath filled with an aqueous solution of phosphoric acid, which was an electrolytic aqueous solution, and the other end of the anode wire was connected to the anode body in the chemical bath. .
  • a uniform dielectric of tantalum oxide (Ta 2 O 5 ) is formed on the surface of the anode body (the surface of the porous sintered body including the inner wall surfaces of the pores) and a part of the surface of the anode wire. form the body layer.
  • poly(3,4-ethylenedioxythiophene) as the second conductive polymer, polystyrene sulfonate, and water were mixed to prepare a second dispersion.
  • the anode body was immersed in the second dispersion, the anode body was lifted out of the second dispersion and subjected to reduced pressure treatment. After the decompression treatment, drying treatment was performed at 80° C. for 20 minutes under atmospheric pressure to form a second conductive polymer layer, thereby obtaining anode bodies A1 to A5.
  • the pressure and the decompression time in the decompression process were changed as shown in Table 1. Further, an anode body was manufactured by the same manufacturing method as that for the anode bodies A1 to A5 without performing the decompression treatment, thereby obtaining the anode body B1.
  • the pressure in the depressurization process is indicated by relative pressure (that is, gauge pressure) based on the atmospheric pressure.
  • the reason why the rate of blistering in the anode body A5 was higher than that in the anode body A1 to A4 is that the moisture contained in the dispersion volatilizes due to the pressure reduction for a long time, making it easy to generate air bubbles. It is considered that the surface conditions of the molecular layer and the first conductive polymer layer deteriorated.
  • the present invention can be used for electrolytic capacitors, preferably for electrolytic capacitors using a porous body as an anode body.
  • Electrolytic capacitor 10 Capacitor element 1: Anode body 2: Anode wire 2a: First part 2b: Second part 3: Dielectric layer 4: Solid electrolyte layer 5: Cathode layer 5a: Carbon layer 5b: Metal paste layer 6: Anode part 7: Cathode part 8: Conductive adhesive 11: Exterior body 13: Anode lead terminal 14: Cathode lead terminal 14a: Joining part

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Un procédé de production d'un condensateur électrolytique selon la présente invention comprend une étape de formation d'une couche d'électrolyte solide, qui contient un polymère conducteur, sur la surface d'un corps d'électrode positive qui est pourvue d'une couche diélectrique. L'étape de formation d'une couche d'électrolyte solide comprend : une première étape dans laquelle une première couche de polymère conducteur qui recouvre la couche diélectrique est formée en imprégnant le corps d'électrode positive d'une première solution, qui contient un premier monomère qui sert de manière première pour un premier polymère conducteur, et en polymérisant le premier monomère sur la surface de la couche diélectrique ; et une seconde étape dans laquelle une seconde couche de polymère conducteur qui recouvre la première couche de polymère conducteur est formée en imprégnant le corps d'électrode positive d'une seconde solution ou d'un second liquide de dispersion, chacun contenant le second polymère conducteur. La seconde étape comprend un traitement à basse pression du corps d'électrode positive.
PCT/JP2022/045965 2021-12-24 2022-12-14 Procédé de production d'un condensateur électrolytique WO2023120309A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010040776A (ja) * 2008-08-05 2010-02-18 Nec Tokin Corp 導電性高分子懸濁液およびその製造方法、導電性高分子材料、電解コンデンサ、ならびに固体電解コンデンサおよびその製造方法
JP2012043958A (ja) * 2010-08-19 2012-03-01 Nec Tokin Corp 固体電解コンデンサおよびその製造方法
WO2017002351A1 (fr) * 2015-06-30 2017-01-05 パナソニックＩｐマネジメント株式会社 Condensateur électrolytique et procédé pour sa fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010040776A (ja) * 2008-08-05 2010-02-18 Nec Tokin Corp 導電性高分子懸濁液およびその製造方法、導電性高分子材料、電解コンデンサ、ならびに固体電解コンデンサおよびその製造方法
JP2012043958A (ja) * 2010-08-19 2012-03-01 Nec Tokin Corp 固体電解コンデンサおよびその製造方法
WO2017002351A1 (fr) * 2015-06-30 2017-01-05 パナソニックＩｐマネジメント株式会社 Condensateur électrolytique et procédé pour sa fabrication

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