WO2022158350A1 - 固体電解コンデンサ素子および固体電解コンデンサ - Google Patents

固体電解コンデンサ素子および固体電解コンデンサ Download PDF

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WO2022158350A1
WO2022158350A1 PCT/JP2022/000738 JP2022000738W WO2022158350A1 WO 2022158350 A1 WO2022158350 A1 WO 2022158350A1 JP 2022000738 W JP2022000738 W JP 2022000738W WO 2022158350 A1 WO2022158350 A1 WO 2022158350A1
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electrolytic capacitor
solid electrolytic
electrolyte layer
solid electrolyte
capacitor element
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French (fr)
Japanese (ja)
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兄 廣田
孝拓 吉井
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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 CN202280010580.5A priority Critical patent/CN116762148A/zh
Priority to JP2022576621A priority patent/JP7734327B2/ja
Priority to US18/258,296 priority patent/US12354812B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode

Definitions

  • the present disclosure relates to solid electrolytic capacitor elements and solid electrolytic capacitors.
  • a solid electrolytic capacitor includes a solid electrolytic capacitor element, a resin exterior or case that seals the solid electrolytic capacitor element, and external electrodes that are electrically connected to the solid electrolytic capacitor element.
  • a solid electrolytic capacitor element includes an anode body, a dielectric layer formed on the surface of the anode body, and a cathode portion covering at least a portion of the dielectric layer.
  • the cathode section has a solid electrolyte layer containing a conductive polymer component covering at least a portion of the dielectric layer.
  • Patent Document 1 discloses an anode comprising at least a valve metal, a dielectric coating formed on the valve metal, and a solid electrolyte layer comprising a conductive polymer formed on the dielectric coating.
  • a conductive polymer is formed by chemical polymerization or electrolytic polymerization.
  • a solid electrolytic capacitor element includes an anode body, a dielectric layer formed on the surface of the anode body, and a cathode section covering at least a portion of the dielectric layer,
  • the cathode portion includes a solid electrolyte layer covering at least a portion of the dielectric layer, the solid electrolyte layer includes a conductive polymer component including a conjugated polymer, and the solid electrolyte layer is heated at 230° C. for 5 hours at 230° C.
  • the oxygen permeability P 1 when heated for a period of time is 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • a solid electrolytic capacitor according to a second aspect of the present disclosure includes at least one solid electrolytic capacitor element described above.
  • FIG. 1 is a cross-sectional schematic diagram of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • the conductive polymer components conjugated polymer, dopant, etc.
  • the conductive polymer components deteriorate due to the action of moisture or oxygen contained in the air.
  • Deterioration of the conductive polymer component reduces the conductivity of the solid electrolyte layer.
  • the orientation of the conjugated polymer in the solid electrolyte layer is low, air is likely to enter when the solid electrolytic capacitor is exposed to high temperatures. Therefore, the deterioration of the conductive polymer component is remarkable especially in a high temperature environment.
  • Solid electrolytic capacitors are sometimes used in high-temperature environments depending on the application. Solid electrolytic capacitors are generally soldered to substrates through a reflow process that exposes them to high temperatures. Therefore, solid electrolytic capacitor elements and solid electrolytic capacitors having excellent heat resistance are desired.
  • the solid electrolytic capacitor element of the first aspect high orientation of the conjugated polymer in the solid electrolyte layer can be obtained.
  • the high orientation of the conjugated polymer improves the crystallinity of the conjugated polymer and stabilizes the conjugated polymer in terms of energy. Therefore, a dense and rigid solid electrolyte layer having excellent film quality can be obtained.
  • the oxygen permeability of the solid electrolyte layer can be kept low, and high electrical conductivity of the solid electrolyte layer can be ensured. Even when exposed to high temperatures, deterioration of the solid electrolyte layer is suppressed, and deterioration of capacitor performance (such as capacitance) can be suppressed. Therefore, high heat resistance of the solid electrolytic capacitor element and the solid electrolytic capacitor can be ensured. By obtaining excellent heat resistance, the reliability of the solid electrolytic capacitor element and the solid electrolytic capacitor can be enhanced.
  • Such a solid electrolyte layer can be formed by triode electrolytic polymerization.
  • Conventional general electropolymerization is carried out by a two-electrode method using an anode body having a dielectric layer formed on its surface as an anode and two electrodes, this anode and a counter electrode.
  • the three-electrode electropolymerization is carried out using an anode body having a dielectric layer formed on its surface as an anode, and using three electrodes: this anode, a counter electrode, and a reference electrode.
  • the use of a reference electrode makes it possible to precisely control the potential of the anode without being affected by changes in the natural potential of the counter electrode.
  • the electropolymerization reaction is controlled more precisely than in the case of the two-electrode system, so the orientation of the conjugated polymer formed by the electropolymerization is enhanced, and the crystallinity is improved. or the conjugated polymer is energetically stabilized.
  • the solid electrolyte layer electropolymerizes a conjugated polymer precursor, optionally in the presence of a dopant, on the surface of the dielectric layer. can be formed by
  • the difference (P 1 ⁇ P 0 ) between the oxygen permeability P 1 and the oxygen permeability P 0 before heating is preferably 0.3 cm 3 /m 2 ⁇ 24 h ⁇ atm or less. , 0.25 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • the heat resistance of the solid electrolytic capacitor element and the solid electrolytic capacitor can be further enhanced. More specifically, even when the solid electrolytic capacitor element is exposed to high temperatures, the oxidation reaction does not progress easily, the deterioration of the solid electrolyte layer is suppressed, high conductivity is maintained, and the capacitor performance (such as capacitance) is improved. ) is further suppressed.
  • the solid electrolytic capacitor element may be heat-treated at a temperature higher than 200°C and lower than or equal to 300°C.
  • a conventional solid electrolytic capacitor element when heat treatment is performed at such a temperature, an oxidation reaction proceeds, and the oxygen permeability is greater than 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm, usually 1.3 cm 3 /m 2 . m 2 ⁇ 24 h ⁇ atm or more.
  • the heat treatment may be performed, for example, for 1 hour or longer.
  • the oxygen permeability of the solid electrolyte layer means the oxygen permeability (cm 3 /m 2.24 h.atm ).
  • the thickness was measured under the same conditions as when forming the solid electrolyte layer of the solid electrolytic capacitor element on one surface of a polyethylene terephthalate (PET) film (length 100 mm x 100 mm x thickness 100 ⁇ m).
  • PET polyethylene terephthalate
  • a sample (sample A) having a solid electrolyte layer of 4 ⁇ m is used.
  • the precoat layer of the solid electrolytic capacitor element when forming a precoat layer, the precoat layer having a thickness of 0.1 ⁇ m is formed before forming the solid electrolyte layer of the sample.
  • Oxygen permeability P1 is the oxygen permeability measured after heating sample A at 230° C. for 5 hours.
  • the solid electrolyte layer of the sample used for measuring the oxygen permeability is formed to have crystallinity of the same degree as that of the solid electrolyte layer of the solid electrolytic capacitor element. That is, the Raman spectrum of the solid electrolyte layer of the sample and the Raman spectrum of the solid electrolyte layer of the solid electrolytic capacitor element may be substantially matched.
  • the full width at half maximum of the peak (first peak) attributed to the CC stretching vibration derived from the conjugated polymer is the Raman spectrum of the solid electrolyte layer of the solid electrolytic capacitor element.
  • the shift amount from the reference position of the first peak of the Raman spectrum of the solid electrolyte layer of the sample is within ⁇ 5% of the shift amount from the reference position of the first peak of the Raman spectrum of the solid electrolyte layer of the solid electrolytic capacitor element.
  • Measurement of oxygen permeability is performed under the following conditions, for example.
  • the solid electrolytic capacitor and the solid electrolytic capacitor element (hereinafter sometimes simply referred to as a capacitor element) of the present disclosure will be described more specifically with reference to the drawings as necessary.
  • a solid electrolytic capacitor comprises one or more capacitor elements. At least one of the capacitor elements included in the solid electrolytic capacitor may have a solid electrolyte layer exhibiting oxygen permeability as described above. It is preferable that 50% or more (more preferably 75% or more) of the number of capacitor elements included in the solid electrolytic capacitor are provided with a solid electrolyte layer exhibiting oxygen permeability as described above. It is more preferable to have a solid electrolyte layer exhibiting oxygen permeability as described above.
  • the anode body can contain a valve action metal, an alloy containing a valve action metal, a compound containing a valve action metal, and the like. These materials can be used singly or in combination of two or more. For example, aluminum, tantalum, niobium, and titanium are preferably used as valve metals.
  • An anode body having a porous surface can be obtained, for example, by roughening the surface of a base material (such as a sheet-like (e.g., foil-like, plate-like) base material) containing a valve metal by etching or the like. . The surface roughening can be performed, for example, by an etching treatment or the like.
  • the anode body may be a molded body of particles containing a valve metal or a sintered body thereof.
  • each of the molded body and the sintered body has a porous structure.
  • Each of the molded body and the sintered body may have a sheet-like shape, a rectangular parallelepiped, a cube, or a shape similar thereto.
  • the anode body usually has an anode lead-out portion and a cathode forming portion.
  • the cathode portion is usually formed on the cathode-forming portion of the anode body with a dielectric layer interposed therebetween.
  • An anode terminal is connected to the anode lead-out portion.
  • the dielectric layer is an insulating layer that functions as a dielectric and is formed so as to cover at least part of the surface of the anode body.
  • the dielectric layer is formed by anodizing the valve action metal on the surface of the anode body by chemical conversion treatment or the like.
  • the dielectric layer may be formed so as to cover at least part of the anode body.
  • a dielectric layer is usually formed on the surface of the anode body. Since the dielectric layer is formed on the porous surface of the anode body, the surface of the dielectric layer has fine irregularities as described above.
  • the dielectric layer contains an oxide of a valve metal.
  • the dielectric layer contains Ta 2 O 5 when tantalum is used as the valve metal, and the dielectric layer contains Al 2 O 3 when aluminum is used as the valve metal. Note that the dielectric layer is not limited to this, as long as it functions as a dielectric.
  • the cathode section has a solid electrolyte layer covering at least a portion of the dielectric layer. Moreover, the cathode section may further include a cathode extraction layer covering at least a portion of the solid electrolyte layer.
  • the cathode part is usually formed on at least part of the surface of the anode body with a dielectric layer interposed therebetween. The solid electrolyte layer and the cathode extraction layer are described below.
  • the solid electrolyte layer is formed on the surface of the anode body so as to cover the dielectric layer with the dielectric layer interposed therebetween.
  • the solid electrolyte layer does not necessarily need to cover the entire dielectric layer (entire surface), and may be formed to cover at least a portion of the dielectric layer.
  • the solid electrolyte layer constitutes at least part of the cathode portion in the solid electrolytic capacitor.
  • a solid electrolyte layer usually contains a conductive polymer component.
  • the conductive polymer component contains at least a conjugated polymer, and may further contain a dopant if necessary.
  • conjugated polymer As the conjugated polymer, a known conjugated polymer used in electrolytic capacitors, such as a ⁇ -conjugated polymer, can be used. Conjugated polymers include, for example, polymers having polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylenevinylene, polyacene, and polythiophenevinylene as a basic skeleton.
  • the above polymer may contain at least one type of monomer unit that constitutes the basic skeleton.
  • the monomer units also include monomer units having substituents.
  • the above polymers include homopolymers and copolymers of two or more monomers.
  • conjugated polymers preferred are conjugated polymers containing monomer units corresponding to at least one selected from the group consisting of pyrrole compounds, thiophene compounds, and aniline compounds.
  • pyrrole compounds include compounds having a pyrrole ring and capable of forming a repeating structure of corresponding monomer units.
  • Thiophene compounds include compounds having a thiophene ring and capable of forming a repeating structure of corresponding monomer units. These compounds can be linked at the 2- and 5-positions of the pyrrole ring or the thiophene ring to form repeating structures of monomeric units, which can form polymers with ⁇ -electron clouds spread throughout the molecule. .
  • aniline compounds include compounds having a benzene ring and at least one (preferably one) amino group bonded to the benzene ring and capable of forming a repeating structure of corresponding monomer units.
  • the aniline compound for example, can form a repeating structure of monomer units by linking an amino group with a CH group p-positioned to the amino group (a CH group that constitutes a benzene ring). , it is possible to form a polymer with a ⁇ -electron cloud spread throughout the molecule.
  • the pyrrole compound may have a substituent at, for example, at least one of the 3- and 4-positions of the pyrrole ring.
  • the thiophene compound may have a substituent at, for example, at least one of the 3- and 4-positions of the thiophene ring.
  • the 3-position substituent and the 4-position substituent may be linked to form a ring condensed to a pyrrole ring or a thiophene ring.
  • the pyrrole compound includes, for example, pyrrole optionally having a substituent at at least one of the 3- and 4-positions.
  • the thiophene compounds include, for example, thiophenes optionally having a substituent at at least one of the 3- and 4-positions, alkylenedioxythiophene compounds (C 2-4 alkylenedioxythiophene compounds such as ethylenedioxythiophene compounds, etc. ).
  • Alkylenedioxythiophene compounds include those having a substituent on the alkylene group portion.
  • Aniline compounds include, for example, anilines which may have a substituent at at least one of the o-position and p-position with respect to the amino group.
  • substituents include alkyl groups (C 1-4 alkyl groups such as methyl group and ethyl group), alkoxy groups (C 1-4 alkoxy groups such as methoxy group and ethoxy group), hydroxy groups, hydroxyalkyl groups ( hydroxy C 1-4 alkyl groups such as hydroxymethyl groups) and the like are preferred, but not limited thereto.
  • substituents include alkyl groups (C 1-4 alkyl groups such as methyl group and ethyl group), alkoxy groups (C 1-4 alkoxy groups such as methoxy group and ethoxy group), hydroxy groups, hydroxyalkyl groups ( hydroxy C 1-4 alkyl groups such as hydroxymethyl groups) and the like are preferred, but not limited thereto.
  • each substituent may be the same or different.
  • a conjugated polymer containing at least monomer units corresponding to pyrrole, or a conjugated system containing at least monomer units corresponding to 3,4-ethylenedioxythiophene compounds such as 3,4-ethylenedioxythiophene (EDOT)
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • the conjugated polymer containing at least a monomer unit corresponding to pyrrole may contain only a monomer unit corresponding to pyrrole, and in addition to the monomer unit, a monomer corresponding to a pyrrole compound other than pyrrole (such as pyrrole having a substituent) May contain units.
  • a conjugated polymer containing at least a monomer unit corresponding to EDOT may contain only a monomer unit corresponding to EDOT, or may contain, in addition to the monomer unit, a monomer unit corresponding to a thiophene compound other than EDOT.
  • the molar ratio of the monomer unit corresponding to the pyrrole compound (or pyrrole) is preferably 50 mol% or more from the viewpoint of easily securing a higher capacitance. , more preferably 75 mol % or more.
  • the molar ratio of monomer units corresponding to the pyrrole compound (or pyrrole) in the conjugated polymer is 100 mol % or less.
  • a conjugated polymer may be composed only of a repeating structure of monomer units corresponding to a pyrrole compound (or pyrrole).
  • the molar ratio of the monomer unit corresponding to the thiophene compound (or EDOT) is preferably 50 mol% or more from the viewpoint of easily securing a higher capacitance. , more preferably 75 mol % or more.
  • the molar ratio of monomer units corresponding to the thiophene compound (or EDOT) in the conjugated polymer is 100 mol % or less.
  • the conjugated polymer may be composed only of a repeating structure of monomer units corresponding to the thiophene compound (or EDOT).
  • Conjugated polymers may be used singly or in combination of two or more.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited, and is, for example, 1,000 or more and 1,000,000 or less.
  • dopant for example, at least one selected from the group consisting of anions and polyanions is used.
  • anions include sulfate ions, nitrate ions, phosphate ions, borate ions, organic sulfonate ions, and carboxylate ions, but are not particularly limited.
  • Dopants that generate sulfonate ions include, for example, p-toluenesulfonic acid and naphthalenesulfonic acid.
  • polyanions include polymer anions.
  • the solid electrolyte layer may contain, for example, a conjugated polymer containing monomer units corresponding to a thiophene compound and a polymer anion.
  • polymer anions even when the solid electrolytic capacitor element is exposed to high temperatures, dedoping is less likely to occur, resulting in higher heat resistance.
  • polymer anions include polymers having multiple anionic groups. Such polymers include polymers containing monomeric units having anionic groups. Examples of anionic groups include sulfonic acid groups and carboxy groups.
  • the anionic group of the dopant may be contained in a free form, an anionic form, or a salt form, or may be contained in a form bound or interacting with the conjugated polymer. .
  • anionic group sulfonic acid group
  • carboxy group sulfonic acid group
  • polymer anions having carboxy groups include, but are not limited to, polyacrylic acid, polymethacrylic acid, and copolymers using at least one of acrylic acid and methacrylic acid.
  • polymer anions having a sulfonic acid group include, for example, polymer-type polysulfonic acids such as polyvinylsulfonic acid, polystyrenesulfonic acid (including copolymers and substituents having substituents), and polyallylsulfonic acid. , polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyestersulfonic acid (aromatic polyestersulfonic acid, etc.), phenolsulfonic acid novolak resins. but not limited to these.
  • the amount of the dopant contained in the solid electrolyte layer is, for example, 10 to 1000 parts by mass, and may be 20 to 500 parts by mass or 50 to 200 parts by mass with respect to 100 parts by mass of the conjugated polymer.
  • the oxygen permeability P 1 of the solid electrolyte layer when heated at 230° C. for 5 hours is 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm or less, preferably 0.9 cm 3 /m 2 ⁇ 24 h ⁇ atm or less, It may be 0.8 cm 3 /m 2 ⁇ 24 h ⁇ atm or less, or may be 0.7 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • the orientation of the conjugated polymer is high, and the conjugated polymer is in a state in which the conjugated polymer is energetically stabilized.
  • Such a solid electrolyte layer has a dense film quality and high electrical conductivity. Therefore, in the solid electrolytic capacitor element and the solid electrolytic capacitor, deterioration of the solid electrolyte layer when exposed to high temperature is suppressed, and deterioration of capacitor performance such as capacitance is suppressed. Therefore, high heat resistance can be obtained.
  • the oxygen permeability P 1 of the solid electrolyte layer is, for example, 0.01 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P 1 of a solid electrolyte layer containing polypyrrole and a dopant (such as naphthalenesulfonic acid) formed by bipolar electropolymerization is higher than 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm. It is 1.3 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P1 of the solid electrolyte layer formed using a liquid dispersion containing polypyrrole and a dopant (polystyrene sulfonic acid or the like) is usually 1.3 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P1 of a solid electrolyte layer formed by chemical polymerization using a polymerization solution containing pyrrole and a dopant (naphthalenesulfonic acid, etc.) is usually 1.5 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P 1 of the solid electrolyte layer containing PEDOT and a dopant (such as polystyrene sulfonic acid) formed by bipolar electropolymerization is higher than 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm, usually 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm. It is 3 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P1 of a solid electrolyte layer formed using a liquid dispersion containing PEDOT and a dopant (such as polystyrene sulfonic acid) is usually 1.3 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability P1 of a solid electrolyte layer formed by chemical polymerization using a polymerization solution containing EDOT and a dopant (such as polystyrene sulfonic acid) is usually 1.5 cm 3 /m 2 ⁇ 24 h ⁇ atm or more.
  • the oxygen permeability of the solid electrolyte layer can be kept low even when exposed to high temperatures.
  • the difference (P 1 -P 0 ) between the oxygen permeability P 1 when heated at 230° C. for 5 hours and the oxygen permeability P 0 before heating is, for example, 0.3 cm 3 /m 2 ⁇ . It is 24 h ⁇ atm or less, and may be 0.25 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • the solid electrolyte layer is inferior in film quality and the oxygen permeability P 1 is large, so the value of (P 1 -P 0 ) is 0.5 cm 3 /m 2 ⁇ 24 h ⁇ atm. becomes a large value exceeding
  • the solid electrolytic capacitor element may be heat-treated at a high temperature exceeding 200°C, for example.
  • the temperature of the heat treatment is, for example, over 200° C. and 300° C. or less, may be 210° C. or more and 300° C. or less, or may be 210° C. or more and 250° C. or less.
  • the film quality of the solid electrolyte layer is inferior, so if heat treatment is performed at such a high temperature, the oxygen permeability of the solid electrolyte layer increases due to the deterioration of the conductive polymer component, and the conductivity increases. decreases. As a result, capacitor performance such as capacitance is degraded.
  • the solid electrolytic capacitor element of the first aspect even if heat treatment is performed at a high temperature, the excellent film quality of the solid electrolyte layer is maintained, and high capacitor performance can be ensured.
  • the heat treatment time is, for example, 1 hour or longer, may be 2 hours or longer, or may be 3 hours or longer.
  • the heat treatment time is, for example, 10 hours or less, and may be 6 hours or less or 5 hours or less.
  • the heat treatment may be performed in the air or in an inert gas atmosphere.
  • the atmosphere for heat treatment can be selected depending on the stage of heat treatment. For example, when the heat treatment is performed after forming the cathode extraction layer, the heat treatment may be performed in the air.
  • the solid electrolyte layer exhibits high crystallinity due to the high orientation of the conjugated polymer. Also, in the solid electrolyte layer, the conjugated polymer is in an energy-stabilized state. Therefore, the solid electrolyte layer exhibits a characteristic Raman spectrum. The Raman spectrum of the solid electrolyte layer will be described in more detail below.
  • the main component of the solid electrolyte layer is a conjugated polymer, and in the Raman spectrum of the solid electrolyte layer, the height of the peak (first peak) attributed to CC stretching vibration derived from the conjugated polymer is the highest. target.
  • the vibrational state of the CC bond changes. At least one of the positions changes. Therefore, based on at least one of the full width at half maximum and the peak position of the first peak attributed to CC stretching vibration, it is possible to grasp the orientation state or energy state of the conjugated polymer in the solid electrolyte layer.
  • the full width at half maximum of the first peak is 80 cm ⁇ 1 or less when the first peak is fitted with the Lorentzian function.
  • the orientation of the conjugated polymer is further enhanced in the solid electrolyte layer, and the film quality can be improved. Therefore, the oxygen permeability of the solid electrolyte layer can be kept low, and high conductivity can be ensured.
  • the oxidation reaction does not progress easily, and the deterioration of the solid electrolyte layer is suppressed. Decrease is suppressed. Reliability can be improved by obtaining high heat resistance of the solid electrolytic capacitor element and the solid electrolytic capacitor.
  • the full width at half maximum of the first peak is, for example, 35 cm ⁇ 1 or more.
  • the solid electrolyte layer can be easily formed.
  • the full width at half maximum of the first peak may be 50 cm ⁇ 1 or more, 55 cm ⁇ 1 or more, or 58 cm ⁇ 1 or more.
  • the oxygen permeability P 1 of the solid electrolyte layer is 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • the position of the first peak is shifted to the low wave number side from the reference position when the solid electrolyte layer is formed by bipolar electrolytic polymerization and heated at 230° C. for 5 hours. It is preferable in some cases. In this case, the orientation of the conjugated polymer is enhanced in the solid electrolyte layer, and the conjugated polymer is in an energy-stabilized state. Therefore, the oxygen permeability of the solid electrolyte layer can be kept low, and high conductivity of the solid electrolyte layer can be easily ensured.
  • the conjugated polymer can be moderately doped with the dopant, it is less likely that the conjugated polymer will be in a reduced state, which also hinders the progress of the oxidation reaction. Reliability can be improved by obtaining high heat resistance of the solid electrolytic capacitor element and the solid electrolytic capacitor.
  • the reference position is the CC expansion/contraction derived from the conjugated polymer in the Raman spectrum of the solid electrolyte layer containing the conjugated polymer formed by the bipolar electropolymerization and heated at 230°C for 5 hours. This is the position of the second peak when fitting the peak attributed to vibration (second peak) with the Lorentzian function.
  • the amount of shift of the position of the first peak from the reference position is usually 0.2% or more, preferably 0.25% or more or 0.3% or more.
  • the shift amount is within such a range, the conjugated polymer in the solid electrolyte layer is energetically stabilized, so that the oxidation reaction hardly progresses.
  • the amount of shift is typically 1% or less, and may be 0.7% or less or 0.51% or less.
  • the conjugated polymer When the shift amount is within such a range, the conjugated polymer can be moderately doped with the dopant, thereby suppressing excessive decomposition of the dopant contained in the solid electrolyte layer. Therefore, high heat resistance can be obtained.
  • the lower limit and upper limit of the shift amount can be combined arbitrarily.
  • the oxygen permeability P 1 when the shift amount of the first peak is within the above range, the oxygen permeability P 1 can be estimated to be 1.0 cm 3 /m 2 ⁇ 24 h ⁇ atm or less.
  • the shift amount is the ratio (%) of the actual shift amount (cm ⁇ 1 ) of the first peak from the reference position when the wave number (cm ⁇ 1 ) at the reference position is 100%.
  • the position of the first peak is preferably 1566 cm -1 or more and 1578 cm -1 or less, more preferably 1570 cm -1 or more and 1577 cm -1 or less.
  • the position of the first peak is preferably 1423 cm -1 or more and 1435 cm -1 or less, more preferably 1429 cm -1 or more and 1434 cm -1 or less. more preferred. In these cases, higher heat resistance of the solid electrolytic capacitor element can be ensured.
  • the solid electrolytic capacitor for determining the reference position the solid electrolyte layer was formed by two-electrode electropolymerization, and except for heating at 230° C. for 5 hours, a comparative three-electrode electropolymerization was used. It is formed under the same conditions as in the case of forming a solid electrolytic capacitor.
  • a liquid composition containing a precursor of a conjugated polymer and, if necessary, a dopant is added to a cathode-forming portion of an anode body having a dielectric layer formed on the surface thereof, and a cathode-forming portion as a counter electrode.
  • a Ti electrode is immersed and a voltage is applied to the anode body so that the potential of the anode body becomes 3.0 V with respect to the silver/silver chloride reference electrode.
  • the pH of the liquid composition is, for example, 3.0.
  • the precursor and dopant of the conjugated polymer are the same components as in the case of forming a solid electrolytic capacitor using three-electrode electropolymerization for comparison. Heating at 230° C. is performed in the air after forming the cathode extraction layer.
  • the full width at half maximum of the first peak may be in the above range (condition a), or the shift amount of the position of the first peak may be in the above range ( Condition b).
  • the solid electrolytic capacitor element may satisfy both condition a and condition b.
  • the Raman spectrum of the solid electrolyte layer of the solid electrolytic capacitor element is measured under the following conditions for the cross section of the solid electrolyte layer at a predetermined position of the solid electrolytic capacitor element.
  • the Raman spectrum of the solid electrolyte layer of Sample A is measured for a cross section of the solid electrolyte layer parallel to the thickness direction at any position of Sample A under the following conditions.
  • Raman spectrometer NanoPhoton RamanFORCE PAV Diffraction grating: 600gr/cm Measurement wavenumber range: 0 cm -1 or more and 2500 cm -1 or less Temperature: 25 ° C
  • the irradiation laser light wavelength, laser power density, and exposure time are determined according to the type of conjugated polymer.
  • the conjugated polymer is polypyrrole
  • the irradiation laser light wavelength is 532 nm
  • the laser power density is 140 W/cm 2
  • the exposure time is 75 seconds.
  • the conjugated polymer is poly(3,4-ethylenedioxythiophene) (PEDOT)
  • the irradiation laser light wavelength is 785 nm
  • the laser power density is 660 W/cm 2
  • the exposure time is 60 seconds.
  • sample B obtained by the following procedure can be used.
  • a solid electrolytic capacitor is embedded in a hardening resin, and the hardening resin is hardened.
  • a cross-section parallel to the thickness direction of the solid electrolyte layer and perpendicular to the length direction of the capacitor element is exposed by subjecting the cured product to polishing or cross-section polishing.
  • the cross section is a cross section at a position of 0 to 0.05 from the end of the solid electrolyte layer opposite to the anode lead-out portion, where the length of the solid electrolyte layer in the direction parallel to the length direction of the capacitor element is 1.
  • sample B a sample for measurement (sample B) is obtained.
  • a portion from the surface of the solid electrolyte layer to a depth of 100 nm (surface layer portion), and holes and depressions (pits) on the surface of the anode body of the solid electrolyte layer. ) is measured on an 8 ⁇ m ⁇ 8 ⁇ m area of the part formed in the .
  • the full width at half maximum and the peak position of the peak attributed to CC stretching vibration are the measured values for six 8 ⁇ m ⁇ 8 ⁇ m regions on the surface layer and 12 8 ⁇ m ⁇ 8 ⁇ m regions formed in the pits of the solid electrolyte layer. is obtained by averaging
  • the cross-section of sample A can be exposed in the same manner as the cross-section of sample B is exposed.
  • the anode body usually has an anode lead-out portion including a first end and a cathode forming portion including a second end.
  • the direction from the first end side to the second end side of the anode body is referred to as the length direction of the anode body or the capacitor element.
  • the length of the solid electrolyte layer is the length in the direction parallel to the length direction of the capacitor element.
  • the direction from the first end side to the second end side of the anode body is a direction parallel to a straight line connecting the center of the end face of the first end and the center of the end face of the second end.
  • the solid electrolyte layer may, if necessary, further contain at least one selected from the group consisting of known additives and known conductive materials other than the conductive polymer component.
  • the conductive material include at least one selected from the group consisting of conductive inorganic materials such as manganese dioxide, and TCNQ complex salts.
  • the solid electrolyte layer may be a single layer or may be composed of multiple layers.
  • the solid electrolyte layer may be configured to include a first solid electrolyte layer covering at least part of the dielectric layer and a second solid electrolyte layer covering at least part of the first solid electrolyte layer.
  • the type, composition, content, etc. of the conductive polymer component and additives contained in each layer may be different or the same in each layer.
  • the solid electrolyte layer can be formed on the surface of the dielectric layer by triode electrolytic polymerization of a conjugated polymer precursor in the presence of a dopant if necessary.
  • electrolytic polymerization is performed in a state in which the cathode-forming portion of an anode body having a dielectric layer formed thereon is immersed in a liquid composition containing a precursor of a conjugated polymer and, if necessary, a dopant.
  • the orientation of the conjugated polymer can be enhanced.
  • the dopant is appropriately doped so that the conjugated polymer can be stabilized in terms of energy. Therefore, high heat resistance of the capacitor element can be ensured.
  • Precursors of conjugated polymers include raw material monomers of conjugated polymers, oligomers and prepolymers in which multiple molecular chains of raw material monomers are linked.
  • One type of precursor may be used, or two or more types may be used in combination. It is preferable to use at least one kind (especially monomer) selected from the group consisting of monomers and oligomers as the precursor, from the viewpoint of easily obtaining higher orientation of the conjugated polymer.
  • a liquid composition usually contains a solvent.
  • solvents include water, organic solvents, and mixed solvents of water and organic solvents (such as water-soluble organic solvents).
  • the liquid composition may optionally contain an oxidizing agent.
  • the oxidizing agent may be applied to the anode body before or after bringing the liquid composition into contact with the anode body on which the dielectric layer is formed.
  • examples of such oxidizing agents include compounds capable of generating Fe 3+ (ferric sulfate, etc.), persulfates (sodium persulfate, ammonium persulfate, etc.), and hydrogen peroxide.
  • the oxidizing agents can be used singly or in combination of two or more.
  • the pH of the liquid composition is, for example, 0.5 or more and 2.5 or less, preferably 0.5 or more and 2 or less, or 1 or more and 2 or less, and may be 1.3 or more and 1.7 or less.
  • the pH of the liquid composition can be adjusted, for example, by adjusting the content of the dopant and the content of the oxidizing agent in the liquid composition.
  • Three-electrode electropolymerization is performed in a state in which the anode body, the counter electrode, and the reference electrode are immersed in the liquid composition.
  • the counter electrode for example, a Ti electrode is used, but it is not limited to this.
  • a silver/silver chloride electrode (Ag/Ag + ) is preferably used as the reference electrode.
  • the voltage (polymerization voltage) applied to the anode body is, for example, 0.6 V or more and 1.5 V or less, may be 0.7 V or more and 1 V or less, or 0.7 V or more and 0.9 V or less. , 0.7 V or more and 0.85 V or less, or 0.7 V or more and 0.8 V or less.
  • the electropolymerization can be performed at such a relatively low polymerization voltage, and the polymerization reaction can be precisely controlled. Therefore, the orientation of the conjugated polymer can be further enhanced.
  • the dopant can be moderately doped.
  • the polymerization voltage is the potential of the anode body with respect to the reference electrode (silver/silver chloride electrode (Ag/Ag + )).
  • a feeder feeder tape or the like
  • a voltage is applied to the anode via the feeder.
  • the potential of the anode body is the potential of a feeder electrically connected to the anode body.
  • the temperature for electrolytic polymerization is, for example, 5°C or higher and 60°C or lower, or may be 15°C or higher and 35°C or lower.
  • a precoat layer may be formed on the surface of the dielectric layer prior to electrolytic polymerization.
  • the precoat layer includes, for example, a conductive material.
  • a precoat layer may be formed using a liquid dispersion containing a conjugated polymer and a dopant.
  • the conjugated polymer of the precoat layer and the conjugated polymer formed by electrolytic polymerization may be of the same type or of different types.
  • the dopant for the precoat layer and the dopant used for electropolymerization may be the same or different.
  • the cathode extraction layer may include at least the first layer that contacts the solid electrolyte layer and covers at least a portion of the solid electrolyte layer, or may include the first layer and the second layer that covers the first layer. good.
  • the first layer include a layer containing conductive particles, a metal foil, and the like.
  • the conductive particles include, for example, at least one selected from conductive carbon and metal powder.
  • the cathode extraction layer may be composed of a layer containing conductive carbon (also referred to as a carbon layer) as the first layer and a layer containing metal powder or metal foil as the second layer. When a metal foil is used as the first layer, the metal foil may constitute the cathode extraction layer.
  • Examples of conductive carbon include graphite (artificial graphite, natural graphite, etc.).
  • the layer containing metal powder as the second layer can be formed, for example, by laminating a composition containing metal powder on the surface of the first layer.
  • a composition containing metal powder such as silver particles and resin (binder resin).
  • resin a thermoplastic resin can be used, but it is preferable to use a thermosetting resin such as an imide resin or an epoxy resin.
  • the type of metal is not particularly limited. It is preferable to use a valve action metal (aluminum, tantalum, niobium, etc.) or an alloy containing a valve action metal for the metal foil. If necessary, the surface of the metal foil may be roughened. The surface of the metal foil may be provided with a chemical conversion coating, or may be provided with a coating of a metal (dissimilar metal) different from the metal constituting the metal foil (dissimilar metal) or a non-metal coating. Examples of dissimilar metals and non-metals include metals such as titanium and non-metals such as carbon (such as conductive carbon).
  • the coating of the dissimilar metal or nonmetal may be used as the first layer, and the metal foil may be used as the second layer.
  • a separator When a metal foil is used for the cathode extraction layer, a separator may be arranged between the metal foil and the anode foil.
  • the separator is not particularly limited, and for example, a nonwoven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (eg, aromatic polyamide such as aliphatic polyamide and aramid) may be used.
  • the solid electrolytic capacitor may be of wound type, chip type or laminated type.
  • a solid electrolytic capacitor may comprise a stack of two or more capacitor elements. The configuration of the capacitor element may be selected according to the type of solid electrolytic capacitor.
  • one end of the cathode terminal is electrically connected to the cathode extraction layer.
  • the cathode terminal is, for example, applied to the cathode lead layer with a conductive adhesive, and bonded to the cathode lead layer via the conductive adhesive.
  • One end of an anode terminal is electrically connected to the anode body.
  • the other end of the anode terminal and the other end of the cathode terminal are pulled out from the resin exterior body or the case, respectively.
  • the other end of each terminal exposed from the resin outer package or the case is used for solder connection with a board on which the solid electrolytic capacitor is to be mounted.
  • the capacitor element is sealed using a resin outer package or case.
  • the material resin e.g., uncured thermosetting resin and filler
  • the capacitor element is sealed with the resin exterior body by transfer molding, compression molding, or the like.
  • the portions on the other end side of the anode terminal and the cathode terminal connected to the anode lead drawn out from the capacitor element are exposed from the mold.
  • the capacitor element is housed in the bottomed case so that the other end portion of the anode terminal and the cathode terminal is located on the opening side of the bottomed case, and the opening of the bottomed case is sealed with the sealing body.
  • the heat treatment can be performed at an appropriate stage after forming the solid electrolyte layer.
  • the heat treatment may be performed after forming the solid electrolyte layer and before forming the cathode lead layer, or after forming the cathode lead layer and before sealing with the resin outer package or case. may be performed after sealing.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a solid electrolytic capacitor according to one embodiment of the present disclosure.
  • a solid electrolytic capacitor 1 includes a capacitor element 2, a resin sheathing body 3 sealing the capacitor element 2, an anode terminal 4 at least partially exposed to the outside of the resin sheathing body 3, and a a cathode terminal 5;
  • the anode terminal 4 and the cathode terminal 5 can be made of metal such as copper or a copper alloy.
  • the resin sheath 3 has a substantially rectangular parallelepiped outer shape
  • the solid electrolytic capacitor 1 also has a substantially rectangular parallelepiped outer shape.
  • Capacitor element 2 includes anode body 6 , dielectric layer 7 covering anode body 6 , and cathode portion 8 covering dielectric layer 7 .
  • the cathode section 8 includes a solid electrolyte layer 9 covering the dielectric layer 7 and a cathode extraction layer 10 covering the solid electrolyte layer 9 .
  • the solid electrolyte layer 9 contains a conductive polymer component containing a conjugated polymer.
  • the anode body 6 includes a region facing the cathode portion 8 and a region not facing the cathode portion 8 .
  • an insulating separation part 13 is formed so as to cover the surface of the anode body 6 in a strip shape. Contact with the body 6 is restricted.
  • the other portion of the region of anode body 6 that does not face cathode portion 8 is electrically connected to anode terminal 4 by welding.
  • the cathode terminal 5 is electrically connected to the cathode section 8 via an adhesive layer 14 made of a conductive adhesive.
  • Solid electrolytic capacitors 1 (solid electrolytic capacitors A1 to A3) shown in FIG. 1 were produced in the following manner, and their characteristics were evaluated.
  • Anode body 6 was produced by roughening both surfaces of an aluminum foil (thickness: 100 ⁇ m) as a base material by etching.
  • Dielectric Layer 7 A cathode forming portion of anode body 6 was immersed in a chemical solution, and a DC voltage of 70 V was applied for 20 minutes to form dielectric layer 7 containing aluminum oxide.
  • a polymerization liquid containing pyrrole (monomer of conjugated polymer), naphthalenesulfonic acid (dopant), and water was prepared.
  • the pH of the polymerization liquid was adjusted as shown in Table 1.
  • Electropolymerization was carried out in a three-electrode system using the resulting polymerization solution. More specifically, the anode body 6 having the precoat layer formed thereon, the counter electrode, and the reference electrode (silver/silver chloride reference electrode) were immersed in the polymerization solution.
  • a voltage was applied to the anode body 6 so that the potential of the anode body 6 with respect to the reference electrode became the polymerization voltage value shown in Table 1, and electrolytic polymerization was performed at 25° C. to form the solid electrolyte layer 9 .
  • a silver paste containing silver particles and a binder resin epoxy resin
  • a binder resin epoxy resin
  • the cathode lead layer 10 composed of the carbon layer 11 and the metal paste layer 12 was formed, and the cathode portion 8 composed of the solid electrolyte layer 9 and the cathode lead layer 10 was formed.
  • a capacitor element 2 was produced as described above.
  • solid electrolytic capacitor 1 (A1 to A4) was completed.
  • a total of 20 solid electrolytic capacitors were produced in the same manner as described above.
  • Solid electrolytic capacitor B1>> In forming the solid electrolyte layer, electrolytic polymerization was performed in a two-electrode system. In the electrolytic polymerization, the anode body on which the precoat layer was formed and the Ti electrode as the counter electrode were immersed in the polymerization liquid, and the potential of the anode body with respect to the silver/silver chloride reference electrode was the value of the polymerization voltage shown in Table 1. A voltage was applied to the anode body such that After forming the cathode extraction layer, heat treatment was performed at 230° C. for 5 hours. Other than these, a total of 20 solid electrolytic capacitors B1 were formed in the same manner as the solid electrolytic capacitor A1.
  • sample A for measuring the oxygen permeability was prepared according to the procedure described above under the same conditions as when forming the solid electrolyte layer of each solid electrolytic capacitor. Using sample A, the oxygen permeability of the solid electrolyte layer was measured according to the procedure described above. In the solid electrolytic capacitors A1 to A3, the oxygen permeability P 0 was measured because the solid electrolyte layer was not heat-treated. For other solid electrolytic capacitors, the oxygen permeability P1 was measured because the heat treatment was performed at 230° C. for 5 hours.
  • an accelerated test was performed by applying the rated voltage to the solid electrolytic capacitor for 2000 hours in a 145°C environment. Thereafter, the capacitance after the accelerated test was measured in a 20° C. environment in the same manner as the initial capacitance, and the average value of 20 solid electrolytic capacitors was obtained.
  • a value obtained by subtracting the initial capacitance from the capacitance after the acceleration test was defined as the capacitance change rate, and the ratio was expressed with the initial capacitance being 100%.
  • the capacitance change rate is a negative value, and the smaller the value, the lower the heat resistance.
  • Table 1 shows the evaluation results.
  • A1 to A6 are examples, and B1 is a comparative example.
  • the oxygen permeability of the solid electrolyte layer is lower than that of the solid electrolytic capacitor B1, and the decrease in capacitance is suppressed.
  • the oxygen permeability P1 when the solid electrolyte layers of the solid electrolytic capacitors A1 to A3 are heated at 230° C. for 5 hours is approximately the same as the oxygen permeability P1 of the solid electrolytic capacitors A4 to A6, respectively. Therefore, it can be said that the oxygen permeability of the solid electrolytic capacitors A1 to A6 is kept low even after the heat treatment.
  • the full width at half maximum of the first peak in the Raman spectrum of the solid electrolyte layer is smaller than that in the solid electrolytic capacitor B1. Also, in the solid electrolytic capacitors A1 to A6, the first peak is shifted from the reference position to the low wave number side. Therefore, in the solid electrolytic capacitors A1 to A6, the crystallinity is improved by increasing the orientation of the conjugated polymer in the solid electrolyte layer, and the copolymeric polymer is energetically stable. It is considered that the film quality of the solid electrolyte layer is improved and the oxygen permeability P0 or P1 is kept low.
  • a solid electrolytic capacitor element and a solid electrolytic capacitor with excellent heat resistance are provided. Therefore, the solid electrolytic capacitor element and the solid electrolytic capacitor can be used in various applications that require high reliability.

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