WO2023190203A1 - 電解コンデンサ - Google Patents

電解コンデンサ Download PDF

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Publication number
WO2023190203A1
WO2023190203A1 PCT/JP2023/011928 JP2023011928W WO2023190203A1 WO 2023190203 A1 WO2023190203 A1 WO 2023190203A1 JP 2023011928 W JP2023011928 W JP 2023011928W WO 2023190203 A1 WO2023190203 A1 WO 2023190203A1
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WIPO (PCT)
Prior art keywords
ether
glycol
electrolytic capacitor
component
capacitor according
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PCT/JP2023/011928
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 茶城
雄一郎 椿
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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 JP2024512385A priority Critical patent/JPWO2023190203A1/ja
Priority to US18/852,224 priority patent/US20250218698A1/en
Priority to CN202380031251.3A priority patent/CN118974864A/zh
Publication of WO2023190203A1 publication Critical patent/WO2023190203A1/ja
Anticipated expiration legal-status Critical
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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
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/145—Liquid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • the present invention relates to an electrolytic capacitor.
  • Hybrid electrolytic capacitors that include a solid electrolyte and a liquid component are seen as promising as capacitors that are small, large in capacity, and have low ESR (equivalent series resistance).
  • Patent Document 1 describes a compound containing polyethylene glycol and a chemical structure of (-CH 2 -CH(R)-O-) n (where R is an alkyl having 1 to 4 carbon atoms) in a capacitor element of a solid electrolytic capacitor. n is an integer).
  • Patent Document 2 proposes an electrolytic solution for electrolytic capacitors in which an organic carboxylic acid salt is dissolved in a mixed solvent containing ⁇ -butyrolactone and glycol ether or diglycol ether.
  • Electrolytic capacitors are used in various temperature environments. On the other hand, liquid components are susceptible to temperature changes. Among these, it is important to maintain the low-temperature characteristics of electrolytic capacitors. For many applications, electrolytic capacitors that can maintain capacitance even at low temperatures (for example, below -50° C.) are required.
  • One aspect of the present invention is an electrolytic capacitor including a capacitor element and a liquid component, wherein the capacitor element includes an anode body having a dielectric layer and a solid electrolyte in contact with the dielectric layer.
  • the liquid component includes a solvent and a solute
  • the solvent includes a glycol ether as a first component
  • the glycol ether is at least one selected from the group consisting of monoalkyl ethers and dialkyl ethers.
  • the glycol ether has a -(CH 2 O) n - structure, and n is an integer of 1 or more.
  • an electrolytic capacitor containing a liquid component that can maintain good capacitance even at low temperatures.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram for explaining the configuration of a capacitor element according to the same embodiment.
  • any of the illustrated lower limits and any of the illustrated upper limits can be arbitrarily combined as long as the lower limit is not greater than the upper limit. .
  • one type may be selected from them and used alone, or two or more types may be used in combination.
  • the term “contains” or “includes” is an expression that includes “contains (or includes),” “substantially consists of,” and “consists of.” It is.
  • electrolytic capacitor may be read as “solid electrolytic capacitor” or “hybrid electrolytic capacitor”. Further, “capacitor” may be read as “capacitor”. Further, “liquid component” may be read as “electrolyte solution” in some cases.
  • An electrolytic capacitor according to an embodiment of the present invention includes a capacitor element and a liquid component.
  • the capacitor element includes an anode body having a dielectric layer.
  • the form of the anode body is not particularly limited.
  • the anode body may be formed of, for example, metal foil or a porous metal sintered body.
  • the surface layer portion of the metal foil may have a porous portion.
  • the surface layer of the metal foil may be roughened by etching.
  • the capacitor element may have a cathode portion.
  • the cathode section includes, for example, a solid electrolyte in contact with a dielectric layer.
  • the solid electrolyte can be a conductive polymer, a conductive inorganic material (such as manganese dioxide), a TCNQ complex, and the like.
  • the liquid component includes a solvent and a solute.
  • the solvent includes a glycol ether as a first component.
  • Glycol ether includes at least one type selected from the group consisting of monoalkyl ether and dialkyl ether (hereinafter also referred to as "glycol ether (G)"). Furthermore, glycol ether (G) has a -(CH 2 O) n - structure, where n is an integer of 1 or more.
  • a monoalkyl ether has an alkyl group at one end, an OH group at the other end, and a main structural group between the alkyl group and the OH group.
  • dialkyl ether has alkyl groups at both ends and has a main structural group between the two alkyl groups.
  • the main structural group has an oxyethylene group or a polyoxyethylene group.
  • Monoalkyl ether has, for example, a structure represented by R-(CH 2 O) n -OH.
  • the dialkyl ether has, for example, a structure represented by R-(CH 2 O) n -R.
  • Two Rs in the dialkyl ether molecule may be the same or different.
  • Glycol ether (G) may be a mixture of multiple types of molecules having different n or different R.
  • glycol ether (G) Unlike glycol compounds which have two OH groups, glycol ether (G) has only one OH group or no OH group at all. Therefore, glycol ether (G) is less susceptible to temperature changes than glycol compounds. By using a liquid component containing glycol ether (G), an electrolytic capacitor that can maintain good capacitance even at low temperatures of, for example, -50° C. or lower can be obtained.
  • the glycol ether (G) is preferably liquid at room temperature (25°C), and preferably has a melting point of at least 0°C or lower.
  • glycol ether (G) it becomes easier to maintain low ESR and dielectric loss tangent (tan ⁇ ) at low temperatures, for example, ⁇ 50° C. or lower. This point is considered to be related to the ability to maintain good ionic conductivity of the liquid component at low temperatures. That is, it is thought that by using glycol ether (G), the low-temperature characteristics of an electrolytic capacitor, for example at -50° C. or lower, are generally improved.
  • the main structural group of the glycol ether (G) may be composed only of an oxyethylene group or a polyoxyethylene group, but may also have an oxyalkylene group other than an oxyethylene group.
  • 60% by mass or more, more preferably 80% by mass or more (may be 100%) of the main structural groups are composed of oxyethylene groups or polyoxyethylene groups.
  • Oxyethylene groups are considered to be more advantageous in improving low-temperature properties than other oxyalkylene groups because they contribute to improving ionic conductivity and have low volatility. It is thought that the higher the ratio of oxygen to carbon in the main structural group, the better the ionic conductivity and the more advantageous it is to increasing the capacity.
  • Glycol ether (G) has a lower probability of forming a hydrogen bond than a glycol compound, and is less likely to cause an esterification reaction to proceed. Therefore, glycol ether (G) is considered to be less affected by temperature changes than glycol compounds. Among these, the formation of hydrogen bonds is considered to be a factor that increases the viscosity of the liquid component at low temperatures and decreases the ionic conductivity of the liquid component.
  • Dialkyl ethers having no OH group are considered to be less susceptible to temperature changes than monoalkyl ethers having one OH group.
  • monoalkyl ethers having one OH group are more difficult to permeate through the sealing member than dialkyl ethers, and therefore are thought to have the effect of significantly suppressing evaporation of the liquid component of the electrolytic capacitor.
  • the content of dialkyl ether in the glycol ether (G) exceeds 50% by mass, and 90% by mass or more may be dialkyl ether.
  • the content of monoalkyl ether in the glycol ether (G) may be 10% by mass or more, and even 20% by mass or more.
  • n may be 1 or more, but the average value of n may be, for example, 3 or more, 4 or more, or 5 or more.
  • the average value of n may be, for example, 20 or less, 15 or less, or 10 or less. If the n value is within such a range, the viscosity of the liquid component containing glycol ether (G) can be maintained lower. Moreover, better ionic conductivity of the liquid component can be maintained. Among them, it is desirable that 90% by mass or more of the glycol ether has an integer n in the range of 1 or more and 11 or less.
  • the alkyl group that glycol ether (G) has (for example, the R group of R-(CH 2 O) n -OH and R-(CH 2 O) n -R) is , a C1-C10 alkyl group having 1 or more and 10 or less carbon atoms.
  • “Cn1-Cn2 alkyl group” is a general term for alkyl groups having carbon numbers n1 (n1 is an integer) to carbon numbers n2 (n2 is an integer larger than n1).
  • C1-C3 alkyl group means at least one selected from the group consisting of methyl group, ethyl group, n-propyl group, and iso-propyl group.
  • the alkyl group (R) may be a C1-C5 alkyl group or a C1-C3 alkyl group.
  • the alkyl groups possessed by the glycol ether (G) may be C1-C10 alkyl groups.
  • the content of glycol ether (G) contained in the liquid component of a certain electrolytic capacitor is x1 mol
  • y mol% of glycol ether (G) is dialkyl ether
  • (100-y) mol% is monoalkyl ether.
  • the liquid component contains (2 ⁇ x1 ⁇ y/100)+(x1 ⁇ (1 ⁇ y/100)) moles of alkyl groups.
  • 0.9 ⁇ (2 ⁇ x1 ⁇ y/100)+(x1 ⁇ (1 ⁇ y/100)) ⁇ moles or more may be a C1-C10 alkyl group, or a C1-C5 alkyl group. It may also be a C1-C3 alkyl group.
  • the alkyl groups of the monoalkyl ether in the glycol ether (G) may be a C1-C10 alkyl group, a C1-C5 alkyl group, or a C1-C3 alkyl group.
  • the alkyl groups in the dialkyl ether may each independently be a C1-C10 alkyl group, a C1-C5 alkyl group, or a C1-C3 alkyl group.
  • the number average molecular weight Mn of the glycol ether (G) may be, for example, 100 or more, 150 or more, or 200 or more.
  • the number average molecular weight Mn may be, for example, 4000 or less, 2000 or less, or 1000 or less. If the number average molecular weight Mn is within such a range, the viscosity of the liquid component containing glycol ether (G) can be maintained lower. Moreover, better ionic conductivity of the liquid component can be maintained.
  • the number average molecular weight of glycol ether is preferably 100 or more and 1000 or less.
  • glycol ether (G) As a solvent, only glycol ether (G) may be used, or components other than glycol ether (G) may be used. However, from the viewpoint of obtaining better capacitance at a low temperature of -50°C or lower, the content of glycol ether (G) in the liquid component may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. It may be % by mass or more. The content of glycol ether (G) in the liquid component may be 95% by mass or less, 90% by mass or less, or 70% by mass or less.
  • the solvent contains at least one component selected from the group consisting of ethylene glycol and sulfolane (hereinafter also referred to as "second component") as a component other than glycol ether (G).
  • second component ethylene glycol and sulfolane
  • ethylene glycol Since ethylene glycol hardly permeates through the sealing member even at high temperatures, it is thought to have the effect of suppressing evaporation of the liquid component of the electrolytic capacitor. Furthermore, when a conductive polymer is used as the solid electrolyte, ethylene glycol is considered to have the effect of improving the crystallinity of the conductive polymer and increasing its conductivity. Furthermore, ethylene glycol has excellent thermal conductivity and excellent heat dissipation when ripple current is generated.
  • Sulfolane is stable at high temperatures and can contribute to lowering the viscosity of the liquid component.
  • Sulfolane can solidify at low temperatures, but by using it in combination with glycol ether (G), it is possible to suppress such a phenomenon while enjoying the benefits of sulfolane.
  • G glycol ether
  • the content of the second component in the liquid component may be, for example, 5% by mass or more, or 20% by mass or more.
  • the content of the second component in the liquid component may be, for example, 90% by mass or less, or 60% by mass or less.
  • the solvent may further contain ⁇ -butyrolactone (hereinafter also referred to as "third component”) as a component other than glycol ether (G).
  • ⁇ -Butyrolactone is stable over a wide temperature range and has a low viscosity.
  • the content of the third component in the liquid component may be, for example, 5% by mass or more, or 20% by mass or more.
  • the content of the third component in the liquid component may be, for example, 70% by mass or less, or 50% by mass or less.
  • the solvent may include a fourth component in addition to the above-mentioned components.
  • a fourth component include glycol compounds other than ethylene glycol, sulfone compounds other than sulfolane, lactone compounds other than ⁇ -butyrolactone, and carbonate compounds.
  • the glycol compound include propylene glycol, trimethylene glycol, 1,4-butanediol, pentanediol, and hexanediol.
  • Examples of the sulfone compound include chain sulfones (dimethylsulfone, diethylsulfone, etc.) and cyclic sulfones (3-methylsulfolane, 3,4-dimethylsulfolane, 3,4-diphenymethylsulfolane, etc.).
  • Examples of lactone compounds include ⁇ -valerolactone.
  • Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.
  • the fourth component may be used alone or in combination of two or more.
  • the mass of the first component may be 0.1 times or more and 5 times or less, or 0.2 times or more and 2 times or less, the mass of the second component.
  • the mass ratio of the first component and the second component By controlling the mass ratio of the first component and the second component, the low-temperature properties can be improved more significantly and in a well-balanced manner.
  • compositions of the solvent of the liquid component include the following.
  • a solvent in which 90% by mass or more of the dialkyl ether in the glycol ether (G) is polyethylene glycol dialkyl ether.
  • (iii) 90% by mass or more of the dialkyl ether in the glycol ether (G) is polyethylene glycol dialkyl ether, and 90 mol% or more of the alkyl groups possessed by the polyethylene glycol dialkyl ether are C1-C10 alkyl groups or C1-C5 A solvent that is an alkyl group or a C1-C3 alkyl group.
  • glycol ether (G) 90% by mass or more of the glycol ether (G) is ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, hexaethylene glycol monomethyl ether, heptaethylene Glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, dodecaethylene glycol monomethyl ether, polyethylene glycol monomethyl ether 400, polyethylene glycol monomethyl ether 550, polyethylene glycol monomethyl ether 1000, polyethylene glycol monomethyl ether 2000, polyethylene glycol monomethyl ether 4000, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 240, ethylene glycol monoethyl ether, diethylene glycol monoethyl
  • glycol ether (G) 90% by mass or more of the glycol ether (G) is polyethylene glycol monomethyl ether 400, polyethylene glycol monomethyl ether 550, polyethylene glycol monomethyl ether 1000, polyethylene glycol monomethyl ether 2000, polyethylene glycol monomethyl ether 4000, polyethylene glycol dimethyl ether 200, A solvent that is at least one selected from the group consisting of polyethylene glycol dimethyl ether 240, polyethylene glycol dimethyl ether 400, polyethylene glycol dimethyl ether 550, polyethylene glycol dimethyl ether 1000, polyethylene glycol dimethyl ether 2000, and polyethylene glycol dimethyl ether 4000.
  • Mn the numerical value of "Mn” in the expression “polyethylene glycol monomethyl ether Mn” or “polyethylene glycol dimethyl ether Mn” indicates an index of number average molecular weight. Mn means a numerical range of Mn ⁇ 0.8 or more and Mn ⁇ 1.2 or less.
  • polyethylene glycol dimethyl ether 400 means polyethylene glycol dimethyl ether having a number average molecular weight of 320 to 480.
  • Mn is a polystyrene-equivalent number average molecular weight calculated using gel permeation chromatography.
  • the solute contains an acid component and a base component.
  • a salt of an acid component and a base component may be used as the solute. At least a portion of the electrolyte salt dissociates in the liquid component to generate cations and anions.
  • the solute contains an acid component and a base component, the degree of ion dissociation increases, so that the repairability of the dielectric layer can be improved.
  • an electrolyte salt may be added to the solvent, an acid component and a base component may be added, or an electrolyte salt and an acid component and/or a base component may be added. Good too.
  • organic acids are preferred.
  • organic acids include organic carboxylic acids or anhydrides thereof.
  • organic acid include aromatic carboxylic acids, aliphatic carboxylic acids, and alicyclic carboxylic acids.
  • aromatic carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, benzoic acid, salicylic acid, trimellitic acid, and pyromellitic acid.
  • alicyclic carboxylic acid include maleic acid and adipic acid.
  • alicyclic carboxylic acids include hydrides of aromatic carboxylic acids. Phthalic acid is preferred from the viewpoint of high repairability and thermal stability of the dielectric layer.
  • One type of acid component may be used alone, or two or more types may be used in combination.
  • an organic base is preferable.
  • the organic base include amine compounds, quaternary amidinium compounds, and quaternary ammonium compounds.
  • the amine compound may be any of primary, secondary, and tertiary amines.
  • Examples of the amine compound include aliphatic amines, aromatic amines, and heterocyclic amines.
  • the base components may be used alone or in combination of two or more.
  • amine compounds include methylamine, dimethylamine, monoethyldimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, N,N-diisopropylethylamine, tetramethylethylenediamine, hexamethylenediamine, spermidine, spermine, amantadine, Examples include aniline, phenethylamine, toluidine, pyrrolidine, piperidine, piperazine, morpholine, imidazole, imidazoline, pyridine, pyridazine, pyrimidine, pyrazine, and 4-dimethylaminopyridine.
  • quaternary amidinium compound a quaternized product of a cyclic amidine compound is preferable, and examples thereof include imidazolium compounds and imidazolinium compounds.
  • examples of quaternary imidazolium compounds include 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium , 1,3-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, and 1,3-diethyl-2-methylimidazolium.
  • Examples of quaternary imidazolinium compounds include 1,3-dimethylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1-ethyl-2,3 -dimethylimidazolinium, 1,3-diethylimidazolinium, 1,2-diethyl-3-methylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,2,3,4-tetra Examples include methylimidazolinium.
  • quaternary ammonium compound for example, diethyldimethylammonium, monoethyltrimethylammonium, etc. are preferable.
  • the molar ratio of the acid component to the base component is preferably 1.1 or more and 10.0 or less.
  • the concentration of the acid component in the liquid component is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less.
  • the concentration of the base component in the liquid component is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less. In these cases, the repairability of the dielectric layer can be further improved.
  • FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor according to the present embodiment
  • FIG. 2 is a partially developed schematic diagram of a capacitor element according to the electrolytic capacitor.
  • a cylindrical electrolytic capacitor will be explained below as an example, the form of the electrolytic capacitor is not particularly limited.
  • the electrolytic capacitor includes, for example, a capacitor element 10, a cylindrical case 11 that houses the capacitor element 10, a sealing member 12 that closes the opening of the case 11, a seat plate 13 that covers the sealing member 12, and a cylindrical case 11 that houses the capacitor element 10. It includes lead wires 14A, 14B led out from the through hole 12a and penetrating the seat plate 13, and lead tabs 15A, 15B connecting the lead wires 14A, 14B to the electrodes of the capacitor element 10. The vicinity of the open end of the case 11 is drawn inward, and the open end is curled so as to be caulked to the sealing member 12.
  • the capacitor element 10 is manufactured from a wound body as shown in FIG.
  • the wound body includes an anode body 21 connected to the lead tab 15A, a cathode body 22 connected to the lead tab 15B, and a separator 23.
  • the wound body is a semi-finished product in which a solid electrolyte is not formed between the anode body 21 and the cathode body 22.
  • FIG. 2 shows a partially unfolded state before the outermost periphery of the wound body is stopped.
  • the anode body 21 includes a metal foil whose surface is roughened so that the surface is uneven or the surface layer is made porous.
  • a dielectric layer is formed on a metal foil having irregularities or porous portions.
  • a solid electrolyte is attached to at least a portion of the surface of the dielectric layer.
  • the solid electrolyte may cover at least a portion of the surface of the cathode body 22 and/or the surface of the separator 23.
  • the capacitor element 10 on which the solid electrolyte is formed is housed in a case 11 together with a liquid component (not shown).
  • liquid component includes a solvent and a solute.
  • Liquid components can be prepared by mixing the components.
  • the liquid component described above may be used as the liquid component.
  • Capacitor element 10 includes an anode body having a dielectric layer, a cathode body, and a solid electrolyte in contact with the dielectric layer. Capacitor element 10 typically includes a separator interposed between an anode body and a cathode body.
  • the anode body may be, for example, a metal foil with a roughened surface.
  • the type of metal constituting the metal foil is not particularly limited, but it is preferable to use valve metals such as aluminum, tantalum, niobium, alloys containing valve metals, etc., since the dielectric layer can be easily formed.
  • the surface of the metal foil can be roughened by a known method. Due to the roughening, a plurality of irregularities are formed on the surface of the metal foil. It is preferable to roughen the surface by etching the metal foil, for example.
  • the etching process may be performed by, for example, a direct current electrolysis method or an alternating current electrolysis method.
  • dielectric layer A dielectric layer is formed on the surface of the anode body. Specifically, since the dielectric layer is formed on the roughened surface of the metal foil, it is formed along the inner wall surface of the hole or pit on the surface of the anode body.
  • the method for forming the dielectric layer is not particularly limited, but it can be formed by chemical conversion treatment of metal foil.
  • the chemical conversion treatment may be performed, for example, by immersing the metal foil in a chemical conversion solution such as an ammonium adipate solution.
  • a voltage may be applied while the metal foil is immersed in the chemical conversion solution.
  • the anode body on which the dielectric layer is formed is prepared by cutting the treated foil into a desired size.
  • Cathode body metal foil is used for the cathode body.
  • the type of metal is not particularly limited, it is preferable to use a valve metal such as aluminum, tantalum, niobium, or an alloy containing a valve metal.
  • the cathode body may be subjected to surface roughening and/or chemical conversion treatment, if necessary. The surface roughening and chemical conversion treatment can be performed, for example, by the method described for the anode body.
  • the separator is not particularly limited, and for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (for example, aliphatic polyamide, aromatic polyamide such as aramid), etc. may be used.
  • the solid electrolyte includes, for example, a conductive polymer.
  • a conductive polymer for example, a ⁇ -conjugated polymer may be used.
  • the conductive polymer may include a ⁇ -conjugated polymer and a dopant.
  • polypyrrole, polythiophene, polyfuran, polyaniline, and derivatives thereof can be used as the ⁇ -conjugated polymer.
  • derivatives refers to a polymer having a basic skeleton of polypyrrole, polythiophene, polyfuran, polyaniline, or the like.
  • polythiophene derivatives include poly(3,4-ethylenedioxythiophene) (PEDOT) and the like.
  • polymers such as polystyrene sulfonic acid (PSS) may be used, naphthalene sulfonic acid, toluene sulfonic acid, etc. may be used.
  • the conductive polymer may be formed, for example, by chemically polymerizing and/or electrolytically polymerizing a conjugated polymer precursor (monomer, oligomer, etc.) on the dielectric layer. At this time, the conjugated polymer precursor and dopant may coexist. A solution in which the conductive polymer (and dopant) is dissolved or a dispersion in which the conductive polymer (and dopant) is dispersed may be applied to the dielectric layer and dried to form a solid electrolyte.
  • a conjugated polymer precursor monomer, oligomer, etc.
  • Capacitor element 10 can be manufactured by a known method.
  • the capacitor element 10 is manufactured by stacking an anode body and a cathode body on which a dielectric layer is formed, with a separator interposed therebetween, and then forming a solid electrolyte layer between the anode body and the cathode body. It's okay.
  • the anode body and the cathode body on which the dielectric layer has been formed are wound together with a separator in between to form a wound body as shown in FIG. 2, and a solid electrolyte is placed between the anode body and the cathode body. It may also be produced by forming layers.
  • the lead wires 14A, 14B may be made to stand up from the winding body as shown in FIG. 2 by winding the winding body while involving the lead tabs 15A, 15B.
  • the outermost end of the outermost layer of the wound body (the cathode body 22 in FIG. 2) is fixed with a winding tape.
  • the capacitor element in the form of a wound body is further subjected to chemical conversion treatment in order to provide a dielectric layer on the cut surface of the anode body. You may go.
  • the electrolytic capacitor can be manufactured by housing the capacitor element 10 and the prepared liquid component in a case 11 and sealing the opening of the case 11 with a sealing member 12.
  • Examples 1 to 8 ⁇ a wound type electrolytic capacitor (diameter 10 mm x length 10 mm) with a rated voltage of 63 V and a rated capacitance of 82 ⁇ F was manufactured. A specific method for manufacturing an electrolytic capacitor will be described below.
  • An Al foil (anode body) with a roughened surface was subjected to a chemical conversion treatment using an ammonium adipate solution to form a dielectric layer.
  • the obtained anode foil was cut into a predetermined size.
  • a lead tab was connected to each of the Al foils serving as the anode foil and the cathode foil, the anode foil and the cathode foil were wound with a separator in between, and the outer surfaces were fixed with a winding tape to produce a wound body.
  • the lead tab and the lead wire integrated with the lead tab were wound while being pulled out from the winding body, and the lead tab was wound around the lead tab.
  • the wound body was further subjected to another chemical conversion treatment using an ammonium adipate solution.
  • the wound body is immersed for 5 minutes in a dispersion containing polyethylenedioxythiophene (conductive polymer), polystyrene sulfonic acid (dopant), and water contained in a specified container, and then the wound body is pulled up from the dispersion. Ta.
  • the wound body impregnated with the dispersion was dried for 20 minutes in a drying oven at 150° C., so that the conductive polymer and the dopant were deposited between the anode foil and the cathode foil of the wound body.
  • the capacitor element was completed and housed in a bottomed cylindrical case with a diameter of 10 mm and a length of 10 mm.
  • a liquid component was injected into the case, and the capacitor element was impregnated with the liquid component in a reduced pressure atmosphere (40 kPa).
  • a solution in which triethylamine phthalate salt was dissolved as a solute (electrolyte salt) in a solvent having the composition shown in Table 1 was used.
  • An electrolytic capacitor was completed by sealing the capacitor element impregnated with the liquid component. Specifically, the capacitor element is housed in a bottomed case so that the lead wires are located on the opening side of the bottomed case, and a sealing member (an elastic material containing butyl rubber as the rubber component) is formed so that the lead wires pass through. ) was placed above the capacitor element, and the capacitor element was sealed in a bottomed case. Then, an electrolytic capacitor as shown in FIG. 1 was completed by drawing near the open end of the bottomed case, curling the open end, and arranging a seat plate in the curled portion. Thereafter, aging treatment was performed while applying a voltage.
  • a sealing member an elastic material containing butyl rubber as the rubber component
  • the electrolytic capacitor according to the present invention has a high capacity even at low temperatures (for example, temperatures below -50°C) and has excellent low-temperature characteristics, so it can be used for various purposes.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2023/011928 2022-03-31 2023-03-24 電解コンデンサ Ceased WO2023190203A1 (ja)

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US18/852,224 US20250218698A1 (en) 2022-03-31 2023-03-24 Electrolytic capacitor
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220344105A1 (en) * 2020-01-30 2022-10-27 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS617616A (ja) * 1984-06-21 1986-01-14 エルナ−株式会社 電解コンデンサ駆動用電解液
JPH0480909A (ja) * 1990-07-24 1992-03-13 Elna Co Ltd 電解コンデンサ駆動用電解液
JPH09106931A (ja) * 1995-10-09 1997-04-22 Hitachi Aic Inc 電解コンデンサ用電解液
WO2019065951A1 (ja) * 2017-09-29 2019-04-04 パナソニックＩｐマネジメント株式会社 電解コンデンサ
JP2021150452A (ja) * 2020-03-18 2021-09-27 三洋化成工業株式会社 ハイブリッド型電解コンデンサ用液状成分及びハイブリッド電解コンデンサ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS617616A (ja) * 1984-06-21 1986-01-14 エルナ−株式会社 電解コンデンサ駆動用電解液
JPH0480909A (ja) * 1990-07-24 1992-03-13 Elna Co Ltd 電解コンデンサ駆動用電解液
JPH09106931A (ja) * 1995-10-09 1997-04-22 Hitachi Aic Inc 電解コンデンサ用電解液
WO2019065951A1 (ja) * 2017-09-29 2019-04-04 パナソニックＩｐマネジメント株式会社 電解コンデンサ
JP2021150452A (ja) * 2020-03-18 2021-09-27 三洋化成工業株式会社 ハイブリッド型電解コンデンサ用液状成分及びハイブリッド電解コンデンサ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220344105A1 (en) * 2020-01-30 2022-10-27 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor
US12112900B2 (en) * 2020-01-30 2024-10-08 Panasonic Intellectual Property Management Co., Ltd. Electrolytic capacitor

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