WO2022085747A1 - 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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Publication number
WO2022085747A1
WO2022085747A1 PCT/JP2021/038852 JP2021038852W WO2022085747A1 WO 2022085747 A1 WO2022085747 A1 WO 2022085747A1 JP 2021038852 W JP2021038852 W JP 2021038852W WO 2022085747 A1 WO2022085747 A1 WO 2022085747A1
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Prior art keywords
conjugated polymer
electrolytic capacitor
solid electrolytic
solid electrolyte
electrolyte layer
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English (en)
French (fr)
Japanese (ja)
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孝拓 吉井
兄 廣田
博美 小澤
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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 CN202180070976.4A priority Critical patent/CN116325044A/zh
Priority to US18/245,301 priority patent/US12368005B2/en
Priority to JP2022557595A priority patent/JP7752360B2/ja
Publication of WO2022085747A1 publication Critical patent/WO2022085747A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • 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
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • This disclosure relates to a solid electrolytic capacitor element and a solid electrolytic capacitor.
  • the solid electrolytic capacitor includes a solid electrolytic capacitor element, a resin exterior or a case for sealing the solid electrolytic capacitor element, and an external electrode electrically connected to the solid electrolytic capacitor element.
  • the solid electrolytic capacitor element includes an anode, a dielectric layer formed on the surface of the anode, and a cathode portion that covers at least a part of the dielectric layer.
  • the cathode portion includes a solid electrolyte layer containing a conductive polymer component that covers at least a part of the dielectric layer.
  • Patent Document 1 is a solid composed of at least an anode made of a valve metal, a dielectric film formed on the valve metal, and a solid electrolyte layer made of a conductive polymer formed on the dielectric film.
  • electrolytic capacitors we are proposing a conductive polymer complexed with a solid electrolytic dielectric ionic polymer in which a conductive polymer is a composite with an ionic polymer.
  • Patent Document 1 describes that a conductive polymer is formed by chemical polymerization or electrolytic polymerization.
  • the solid electrolytic capacitor element includes an anode, a dielectric layer formed on the surface of the anode, and a cathode portion covering at least a part of the dielectric layer.
  • the cathode portion covers at least a part of the dielectric layer and includes a solid electrolyte layer containing a conjugated polymer.
  • the cathode portion belongs to CC expansion / contraction vibration derived from the conjugated polymer.
  • the solid electrolytic capacitor element includes an anode, a dielectric layer formed on the surface of the anode, and a cathode portion covering at least a part of the dielectric layer.
  • the cathode portion covers at least a part of the dielectric layer and includes a solid electrolyte layer containing a conjugated polymer.
  • the Raman spectrum of the solid electrolyte layer it belongs to CC expansion and contraction vibration derived from the conjugated polymer.
  • the first peak is fitted by the Lorentz function, the position of the first peak is shifted from the reference position to the low frequency side by 0.2% or more and 1% or less, and the reference position is a two-pole type.
  • the Raman spectrum of the solid electrolyte layer containing the conjugated polymer formed by electrolytic polymerization the second peak attributed to the CC expansion and contraction vibration derived from the conjugated polymer is fitted by the Lorentz function. The position of the peak.
  • the solid electrolytic capacitor according to the third aspect of the present disclosure includes at least one of the above solid electrolytic capacitor elements.
  • FIG. 1 is a schematic cross-sectional view of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • the problems in the prior art will be briefly described below.
  • the conductive polymer component conjugated polymer, dopant, etc.
  • the conductivity of the solid electrolyte layer is increased. Sex may be reduced.
  • the orientation of the conjugated polymer in the solid electrolyte layer is low, cracks occur in the solid electrolyte layer when the solid electrolytic capacitor is exposed to a high temperature, and air easily invades. Therefore, the conductive polymer component Is likely to deteriorate. Deterioration of the conductive polymer component is particularly remarkable in a high temperature environment.
  • Solid electrolytic capacitors may be used in high temperature environments depending on the application. Further, the solid electrolytic capacitor is generally solder-bonded to the substrate through a reflow process exposed to a high temperature. Therefore, there is a demand for a solid electrolytic capacitor element and a solid electrolytic capacitor that suppress deterioration of the conductive polymer component even in a high temperature environment and have excellent heat resistance.
  • the peak (first peak) attributed to the CC expansion and contraction vibration derived from the conjugated polymer is a Lorentz function.
  • the half-value total width of the first peak at the time of fitting is controlled to 35 cm -1 or more and 80 cm -1 or less.
  • the position of the first peak is 0.2 from the reference position to the low wavenumber side. It is controlled so that the state is shifted by% or more and 1% or less.
  • the reference position is the peak (second peak) attributed to the CC expansion and contraction vibration derived from the conjugated polymer in the Raman spectrum of the solid electrolyte layer containing the conjugated polymer formed by the bipolar electrolytic polymerization. ) Is the position of the second peak when fitted with the Lorenz function.
  • the high orientation of the conjugated polymer in the solid electrolyte layer can be ensured, and a dense and rigid solid electrolyte layer having excellent film quality can be obtained. Therefore, high conductivity of the solid electrolyte layer can be ensured.
  • the conjugated polymer is energetically stabilized in the solid electrolyte layer. Therefore, high conductivity of the solid electrolyte layer can be ensured.
  • the solid electrolyte layer can be formed by a three-pole electrolytic polymerization.
  • Conventional general electrolytic polymerization is carried out by a two-pole system in which an anode having a dielectric layer formed on its surface is used as an anode and two electrodes, an anode and a counter electrode, are used.
  • the tripolar electrolytic polymerization is carried out by using an anode having a dielectric layer formed on the surface as an anode and using three electrodes of this anode, a counter electrode and a reference electrode.
  • the potential of the anode can be precisely controlled without being affected by the change in the natural potential of the counter electrode. Therefore, in the case of the three-pole type, the electrolytic polymerization reaction is controlled more precisely than in the case of the two-pole type, so that the orientation of the conjugated polymer formed by the electrolytic polymerization is enhanced and the crystallinity is improved. It is improved and the conjugated polymer is energetically stabilized. Therefore, on the first side surface, the full width at half maximum of the first peak is 35 cm -1 or more and 80 cm -1 or less (condition a).
  • the position of the first peak is 0.2% on the low wavenumber side of the position of the second peak (that is, the reference position) with respect to the solid electrolyte layer formed by the bipolar electrolytic polymerization. Shift by 1% or less (condition b).
  • the solid electrolyte layer electrolytically polymerizes the precursor of the conjugated polymer on the surface of the dielectric layer in the presence of the dopant, if necessary. It can be formed by.
  • the dopant is easily doped into the conjugated polymer appropriately, the reduced state of the conjugated polymer is reduced, so that the progress of the oxidation reaction is hindered and the heat resistance is high. Is obtained.
  • 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 attributed to the CC expansion and contraction vibration derived from the conjugated polymer is the highest and characteristic.
  • the vibration state of the CC bond changes, so the half-value full width and peak position of the peak attributed to CC expansion and contraction vibration At least one changes. Therefore, it is possible to grasp the orientation state or energy state of the conjugated polymer in the solid electrolyte layer based on at least one of the half-value full width and the peak position of the first peak attributed to the CC expansion and contraction vibration.
  • the Raman spectrum of the solid electrolyte layer is measured with respect to the cross section of the solid electrolyte layer at a predetermined position of the solid electrolytic capacitor element under the following conditions.
  • Raman spectroscope NanoPhotoon RamanFORCE PAV Diffraction grating: 600 gr / cm Wavenumber range: 0 cm -1 or more 2500 cm -1 or less Temperature: 25 ° C
  • the irradiation laser light wavelength, the laser output density, and the exposure time are determined according to the type of the conjugated polymer. For example, when the conjugated polymer is polypyrrole, the irradiation laser light wavelength is 532 nm, the laser output density is 140 W / cm 2 , and the exposure time is 75 seconds. When the conjugated polymer is poly (3,4-ethylenedioxythiophene) (PEDOT), the irradiation laser light wavelength is 785 nm, the laser output density is 660 W / cm 2 , and the exposure time is 60 seconds.
  • the solid electrolytic capacitor is embedded in the curable resin to cure the curable resin.
  • 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.
  • the cross section is a cross section at a position of 0 to 0.05 from the end opposite to the anode extraction portion of the solid electrolyte layer, where 1 is the length of the solid electrolyte layer in the direction parallel to the length direction of the condenser element.
  • sample A is obtained.
  • a portion (surface layer portion) from the surface of the solid electrolyte layer to a depth of 100 nm, and holes and dents (pits) on the surface of the anode body of the solid electrolyte layer may be referred to.
  • the Raman spectrum is measured for an 8 ⁇ m ⁇ 8 ⁇ m region of the portion formed in).
  • the full width at half maximum and peak position of the peak attributed to CC expansion and contraction vibrations are measured values for 6 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 anode body usually has an anode extraction portion including a first end portion and a cathode forming portion including a second end portion.
  • 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 the linear direction connecting the center of the end face of the first end and the center of the end face of the second end.
  • the solid electrolytic capacitor and the solid electrolytic capacitor element (hereinafter, may be simply referred to as a capacitor element) of the present disclosure will be described more specifically with reference to the drawings as necessary.
  • Solid electrolytic capacitors include one or more capacitor elements. At least one of the capacitor elements included in the solid electrolytic capacitor may be provided with a solid electrolyte layer that satisfies at least one of the condition a and the condition b. In 50% or more (more preferably 75% or more) of the number of capacitor elements contained in the solid electrolytic capacitor, it is preferable to have a solid electrolyte layer satisfying at least one of the conditions a and b, and all the capacitor elements. It is more preferable to have a solid electrolyte layer satisfying at least one of the condition a and the condition b.
  • the anode body can include a valve acting metal, an alloy containing a valve acting metal, a compound containing a valve acting metal, and the like. These materials can be used alone or in combination of two or more.
  • the valve acting metal for example, aluminum, tantalum, niobium, and titanium are preferably used.
  • An anode having a porous surface can be obtained by roughening the surface of a base material containing a valve acting metal (for example, a sheet-like (for example, foil-like or plate-like) base material) by etching or the like. .. The roughening can be performed by, for example, an etching process.
  • the anode body may be a molded body of particles containing a valve acting 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 extraction portion and a cathode forming portion.
  • the cathode portion is usually formed in the cathode forming portion of the anode body via the dielectric layer.
  • An anode terminal is connected to the anode lead-out portion.
  • the dielectric layer is an insulating layer that functions as a dielectric formed so as to cover the surface of at least a part of the anode.
  • the dielectric layer is formed by anodizing the valve acting 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 a part of the anode body.
  • the dielectric layer is usually formed on the surface of the anode. Since the dielectric layer is formed on the porous surface of the anode body, the surface of the dielectric layer has a fine uneven shape as described above.
  • the dielectric layer contains an oxide of the valve acting metal.
  • the dielectric layer when tantalum is used as the valve acting metal contains Ta 2 O 5
  • the dielectric layer when aluminum is used as the valve acting metal contains Al 2 O 3 .
  • the dielectric layer is not limited to this, and may be any one that functions as a dielectric.
  • the cathode portion includes a solid electrolyte layer that covers at least a part of the dielectric layer. Further, the cathode portion may further include a cathode extraction layer that covers at least a part of the solid electrolyte layer. The cathode portion is usually formed on the surface of at least a part of the anode body via a dielectric layer.
  • the solid electrolyte layer and the cathode extraction layer will be described.
  • the solid electrolyte layer is formed on the surface of the anode body so as to cover the dielectric layer via the dielectric layer.
  • the solid electrolyte layer does not necessarily have to cover the entire dielectric layer (entire surface), and may be formed so as to cover at least a part of the dielectric layer.
  • the solid electrolyte layer constitutes at least a part of the cathode portion of the solid electrolytic capacitor.
  • the 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 known ones used for electrolytic capacitors, for example, a ⁇ -conjugated polymer can be used.
  • conjugated polymer include polymers having polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, and polythiophene vinylene as basic skeletons.
  • the polymer may contain at least one monomer unit constituting the basic skeleton.
  • the above polymers also include homopolymers, copolymers of two or more monomers, and derivatives thereof (such as substituents having substituents).
  • conjugated polymers a conjugated polymer containing a monomer unit corresponding to a pyrrole compound, a conjugated polymer containing a monomer unit corresponding to a thiophene compound, and the like are preferable.
  • the pyrrole compound include compounds having a pyrrole ring and capable of forming a repeating structure of the corresponding monomer unit.
  • the thiophene compound include compounds having a thiophene ring and capable of forming a repeating structure of the corresponding monomer unit. These compounds can be linked at the 2- and 5-positions of the pyrrole or thiophene rings to form a repeating structure of monomer units, which allows the formation of a polymer in which the ⁇ electron cloud spreads throughout the molecule. ..
  • the pyrrole compound may have, for example, a substituent at at least one of the 3-position and the 4-position of the pyrrole ring.
  • the thiophene compound may have, for example, a substituent at at least one of the 3-position and the 4-position of the thiophene ring.
  • the substituent at the 3-position and the substituent at the 4-position may be linked to form a ring condensing on a pyrrole ring or a thiophene ring.
  • Examples of the pyrrole compound include pyrrole which may have a substituent at at least one of the 3-position and the 4-position.
  • thiophene compound examples include thiophene which may have a substituent at at least one of the 3-position and 4-position, an alkylenedioxythiophene compound (C 2-4 alkylenedioxythiophene compound such as an ethylenedioxythiophene compound, and the like). ).
  • alkylenedioxythiophene compound also includes those having a substituent in the portion of the alkylene group.
  • substituents examples include an alkyl group (C 1-4 alkyl group such as methyl group and ethyl group), an alkoxy group (C 1-4 alkoxy group such as methoxy group and ethoxy group), a hydroxy group and a hydroxyalkyl group (hydroxyalkyl group).
  • a hydroxy C 1-4 alkyl group such as a hydroxymethyl group) is preferable, but the present invention is not limited thereto.
  • the respective substituents may be the same or different.
  • a conjugated polymer containing at least a monomer unit corresponding to pyrrole or a conjugated system containing at least a monomer unit corresponding to a 3,4-ethylenedioxythiophene compound (such as 3,4-ethylenedioxythiophene (EDOT)).
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT polymer
  • the conjugated polymer containing at least the monomer unit corresponding to pyrrole may contain only the monomer unit corresponding to pyrrole, and in addition to the monomer unit, the monomer corresponding to a pyrrole compound other than pyrrole (such as pyrrole having a substituent). It may include a unit.
  • the conjugated polymer containing at least the monomer unit corresponding to EDOT may contain only the monomer unit corresponding to EDOT, and may contain the monomer unit corresponding to the thiophene compound other than EDOT in addition to the monomer unit.
  • the molar ratio of the monomer unit corresponding to the pyrrole compound (or pyrrole) is preferably 90 mol% or more from the viewpoint of easily securing a higher capacitance. ..
  • the molar ratio of the monomer unit corresponding to the pyrrole compound (or pyrrole) in the conjugated polymer is 100 mol% or less.
  • the conjugated polymer may be composed only of a repeating structure of a monomer unit corresponding to a pyrrole compound (or pyrrole).
  • the molar ratio of the monomer unit corresponding to the thiophene compound (or EDOT) is preferably 90 mol% or more from the viewpoint of easily securing a higher capacitance. ..
  • the molar ratio of the monomer unit corresponding to the thiophene compound (or EDOT) in the conjugated polymer is 100 mol% or less.
  • the conjugated polymer may be composed of only the repeating structure of the monomer unit corresponding to the thiophene compound (or EDOT).
  • conjugated polymer one type may be used alone, or two or more types may be used in combination.
  • the weight average molecular weight (Mw) of the conjugated polymer is not particularly limited, but is, for example, 1,000 or more and 1,000,000 or less.
  • the weight average molecular weight (Mw) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). GPC is usually measured using a polystyrene gel column and water / methanol (volume ratio 8/2) as a mobile phase.
  • Dopant for example, at least one selected from the group consisting of anions and polyanions is used.
  • anion examples include sulfate ion, nitrate ion, phosphate ion, borate ion, organic sulfonic acid ion, carboxylic acid ion and the like, but are not particularly limited.
  • dopants that generate sulfonic acid ions include p-toluenesulfonic acid and naphthalenesulfonic acid.
  • polyanions include polymer anions.
  • the solid electrolyte layer may contain, for example, a conjugated polymer containing a monomer unit corresponding to the thiophene compound and a polymer anion.
  • a conjugated polymer containing a monomer unit corresponding to the thiophene compound and a polymer anion.
  • Examples of the polymer anion include a polymer having a plurality of anionic groups. Examples of such a polymer include those containing a monomer unit having an anionic group. Examples of the anionic group include a sulfonic acid group and a carboxy group.
  • 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 bonded or interacted with a conjugated polymer. .. In the present specification, all of these forms are included and may be simply referred to as an "anionic group", a “sulfonic acid group”, a “carboxy group” and the like.
  • polymer anion having a carboxy group examples include, but are not limited to, a copolymer using at least one of polyacrylic acid, polymethacrylic acid, acrylic acid and methacrylic acid.
  • polymer anion having a sulfonic acid group examples include, for example, polyvinyl sulfonic acid, polystyrene sulfonic acid (including copolymers and substituents having a substituent), and polyallyl sulfonic acid as polymer-type polysulfonic acids.
  • polyvinyl sulfonic acid examples include, for example, polyvinyl sulfonic acid, polystyrene sulfonic acid (including copolymers and substituents having a substituent), and polyallyl sulfonic acid as polymer-type polysulfonic acids.
  • 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 full width at half maximum of the first peak is, for example, 80 cm -1 or less.
  • the full width at half maximum of the first peak is 35 cm -1 or more. In this case, the solid electrolyte layer can be easily formed. From the viewpoint of obtaining higher orientation and higher heat resistance, 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 position of the first peak shifts to the low wavenumber side from the reference position when the solid electrolyte layer is formed by bipolar electrolytic polymerization.
  • the shift amount at this time is usually 0.2% or more, preferably 0.25% or more or 0.3% or more.
  • the conjugated polymer is energetically stabilized in the solid electrolyte layer, so that the oxidation reaction is difficult to proceed.
  • the dopant is likely to be appropriately doped into the conjugated polymer, so that the conjugated polymer is less likely to be in a reduced state. Therefore, high heat resistance can be obtained.
  • the shift amount is usually 1% or less, and may be 0.7% or less or 0.51% or less.
  • the shift amount is in such a range, the dopant is likely to be appropriately doped into the conjugated polymer, so that the decomposition of the dopant contained in the solid electrolyte layer is suppressed from becoming excessively large. Therefore, high heat resistance can be obtained.
  • the lower limit value and the upper limit value of the shift amount can be arbitrarily combined.
  • the position of the first peak is preferably 1566 cm -1 or more and 1578 cm -1 or less, and 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, and 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 electrolyte layer may 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 a conductive inorganic material such as manganese dioxide and a TCNQ complex salt.
  • the solid electrolyte layer may be a single layer or may be composed of a plurality of layers.
  • the solid electrolyte layer may be configured to include a first solid electrolyte layer that covers at least a part of the dielectric layer and a second solid electrolyte layer that covers at least a part of the first solid electrolyte layer.
  • the type, composition, content, etc. of the conductive polymer component, the additive, etc. contained in each layer may be different or the same in each layer.
  • a layer for enhancing adhesion (for example, a precoat layer made of a conductive material) may be interposed between the dielectric layer and the solid electrolyte layer.
  • the solid electrolyte layer can be formed by electrolytically polymerizing a precursor of a conjugated polymer on the surface of the dielectric layer in the presence of a dopant, if necessary, in a triode manner.
  • electrolytic polymerization is carried out in a state where the cathode forming portion of the anode having a dielectric layer formed on the surface is immersed in a liquid mixture 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, and the conjugated polymer can be energetically stabilized. Therefore, high heat resistance of the capacitor element can be ensured.
  • Examples of the precursor of the conjugated polymer include a raw material monomer of the conjugated polymer, an oligomer in which a plurality of molecular chains of the raw material monomer are connected, and a prepolymer.
  • One type of precursor may be used, or two or more types may be used in combination. From the viewpoint that higher orientation of the conjugated polymer can be easily obtained, it is preferable to use at least one selected from the group consisting of monomers and oligomers (particularly, monomers) as the precursor.
  • the liquid mixture usually contains a solvent.
  • the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent (such as a water-soluble organic solvent).
  • a dopant When a dopant, other conductive material, additive, etc. are used, they may be added to the liquid mixture.
  • the liquid component may contain an oxidizing agent, if necessary. Further, the oxidizing agent may be applied to the anode body before or after the liquid mixture is brought into contact with the anode body on which the dielectric layer is formed.
  • an oxidizing agent include sulfates, sulfonic acids, and salts thereof. Oxidizing agents may be used alone or in combination of two or more.
  • the sulfate include a salt of sulfuric acid such as ferric sulfate and sodium persulfate, and a salt of sulfuric acid such as persulfuric acid and a metal.
  • the metal constituting the salt include alkali metals (sodium, potassium, etc.), iron, copper, chromium, and zinc.
  • Sulfonic acid or a salt thereof has a function as a dopant in addition to a function as an oxidizing agent.
  • sulfonic acid or a salt thereof low-molecular-weight sulfonic acid or a salt thereof exemplified for other dopants may be used.
  • the pH of the liquid mixture 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.
  • the pH of the liquid mixture can be adjusted, for example, by adjusting the content of the dopant in the liquid mixture, the content of the oxidizing agent, and the like.
  • the three-pole electrolytic polymerization is carried out in a state where the anode, the counter electrode and the reference electrode are immersed in the liquid mixture.
  • the counter electrode for example, a Ti electrode is used, but the counter electrode is not limited to this.
  • the reference electrode it is preferable to use a silver / silver chloride electrode (Ag / Ag + ).
  • the voltage (polymerization voltage) applied to the anode is, for example, 0.6 V or more and 1.5 V or less, 0.7 V or more and 1 V or less, and 0.7 V or more and 0.9 V or less. May be.
  • the polymerization voltage is the potential of the anode with respect to the reference electrode (silver / silver chloride electrode (Ag / Ag + )).
  • a feeding body (feeding tape or the like) is electrically connected to the anode drawing portion, and a voltage is applied to the anode body via the feeding body.
  • the electric potential of the anode body is the electric potential of the feeding body electrically connected to the anode body.
  • the temperature at which electrolytic polymerization is performed is, for example, 5 ° C. or higher and 60 ° C. or lower, and may be 15 ° C. or higher and 35 ° C. or lower.
  • the cathode extraction layer may include at least a first layer that comes into contact with the solid electrolyte layer and covers at least a part of the solid electrolyte layer, and may include a first layer and a 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 at least one selected from conductive carbon and metal powder.
  • the cathode drawer layer may be formed by a layer containing conductive carbon as the first layer (also referred to as a carbon layer) and a layer containing metal powder or a metal foil as the second layer. When a metal foil is used as the first layer, the cathode drawer layer may be formed of this metal foil.
  • Examples of the conductive carbon include graphite (artificial graphite, natural graphite, etc.).
  • the layer containing the metal powder as the second layer can be formed, for example, by laminating a composition containing the metal powder on the surface of the first layer.
  • a second layer include a metal paste layer formed by using a composition containing a metal powder such as silver particles and a resin (binder resin).
  • a resin binder 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, but it is preferable to use a valve acting metal such as aluminum, tantalum, niobium, or an alloy containing a valve acting metal. If necessary, the surface of the metal foil may be roughened.
  • the surface of the metal foil may be provided with a chemical conversion film, or may be provided with a metal (dissimilar metal) or non-metal film different from the metal constituting the metal foil. Examples of the dissimilar metal and the non-metal include a metal such as titanium and a non-metal such as carbon (conductive carbon and the like).
  • the above-mentioned dissimilar metal or non-metal (for example, conductive carbon) coating may be used as the first layer, and the above-mentioned metal foil may be used as the second layer.
  • a separator When the metal foil is used for the cathode drawer layer, a separator may be arranged between the metal foil and the anode foil.
  • the separator is not particularly limited, and for example, a non-woven fabric containing fibers of cellulose, polyethylene terephthalate, vinylon, polyamide (for example, aromatic polyamide such as aliphatic polyamide and aramid) may be used.
  • the solid electrolytic capacitor may be a wound type and may be a chip type or a laminated type.
  • a solid electrolytic capacitor may include a laminate of two or more capacitor elements. The configuration of the capacitor element may be selected according to the type of the solid electrolytic capacitor.
  • one end of the cathode terminal is electrically connected to the cathode extraction layer.
  • the cathode terminal is, for example, coated with a conductive adhesive on the cathode drawer layer and bonded to the cathode drawer layer via the conductive adhesive.
  • One end of the 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 drawn out from the resin exterior or the case, respectively.
  • the other end of each terminal exposed from the resin exterior or the case is used for solder connection with a substrate on which a solid electrolytic capacitor should be mounted.
  • the capacitor element is sealed using a resin exterior or a case.
  • the material resin of the condenser element and the exterior body (for example, uncured thermosetting resin and filler) is housed in a mold, and the condenser element is sealed with the resin exterior body by a transfer molding method, a compression molding method, or the like. You may. At this time, 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, respectively.
  • the capacitor element is housed in the bottomed case so that the other end side 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 a sealant. May form a solid electrolytic capacitor.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • the solid electrolytic capacitor 1 includes a capacitor element 2, a resin exterior body 3 that seals the capacitor element 2, an anode terminal 4 in which at least a part thereof is exposed to the outside of the resin exterior body 3, and the like. It is provided with a cathode terminal 5.
  • the anode terminal 4 and the cathode terminal 5 can be made of a metal such as copper or a copper alloy.
  • the resin exterior body 3 has a substantially rectangular parallelepiped outer shape, and the solid electrolytic capacitor 1 also has a substantially rectangular parallelepiped outer shape.
  • the capacitor element 2 includes an anode body 6, a dielectric layer 7 covering the anode body 6, and a cathode portion 8 covering the dielectric layer 7.
  • the cathode portion 8 includes a solid electrolyte layer 9 that covers the dielectric layer 7, and a cathode extraction layer 10 that covers the solid electrolyte layer 9.
  • the solid electrolyte layer 9 contains 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 portion 13 is formed so as to cover the surface of the anode body 6 in a band shape, and the cathode portion 8 and the anode portion 8 and the anode portion are formed. Contact with body 6 is restricted.
  • the other part of the region of the anode body 6 that does not face the cathode portion 8 is electrically connected to the anode terminal 4 by welding.
  • the cathode terminal 5 is electrically connected to the cathode portion 8 via an adhesive layer 14 formed of a conductive adhesive.
  • Solid Electrolytic Capacitors A1 to A4 The solid electrolytic capacitors 1 (solid electrolytic capacitors A1 to A4) shown in FIG. 1 were manufactured in the following manner, and their characteristics were evaluated.
  • the anode body 6 was prepared by roughening the surfaces of both aluminum foils (thickness: 100 ⁇ m) as a base material by etching.
  • a polymerization solution containing pyrrole (monomer of conjugated polymer), naphthalene sulfonic acid (dampon), and water was prepared.
  • naphthalene sulfonic acid By adjusting the amount of naphthalene sulfonic acid added, the pH of the polymerization solution was adjusted as shown in Table 1.
  • electrolytic polymerization was carried out by a tripolar method. More specifically, the anode body 6 on which the precoat layer was formed, 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 was the value of the polymerization voltage 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) is applied to the surface of the carbon layer 11 and heated at 150 to 200 ° C. for 10 to 60 minutes to cure the binder resin, and the metal paste layer 12 Formed.
  • the cathode extraction 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 extraction layer 10 was formed.
  • the capacitor element 2 was manufactured as described above.
  • a resin exterior body 3 made of an insulating resin was formed around the capacitor element 2 by molding. At this time, the other end of the anode terminal 4 and the other end of the cathode terminal 5 are in a state of being pulled out from the resin exterior body 3.
  • solid electrolytic capacitors 1 (A1 to A5) were completed.
  • a total of 20 solid electrolytic capacitors were manufactured.
  • Solid Electrolytic Capacitor A5 A mixed solution was prepared by dissolving 3,4-ethylenedioxythiophene monomer and polystyrene sulfonic acid (PSS, Mw: 160 ⁇ 10 3 ) as a polymer anion in ion-exchanged water. A polymer solution was prepared by adding iron (III) sulfate (oxidizing agent) dissolved in ion-exchanged water while stirring the mixed solution. A total of 20 solid electrolytic capacitors A5 were produced in the same manner as the solid electrolytic capacitors A1 to A4 except that the obtained polymer solution was used.
  • Solid Electrolytic Capacitor B1 A total of 20 solid electrolytic capacitors B1 were formed in the same manner as the solid electrolytic capacitors A1 to A4 except that electrolytic polymerization was performed by a two-pole method.
  • electrolytic polymerization the anode on which the precoat layer is formed and the Ti electrode as the counter electrode are immersed in the polymerization solution, and the potential of the anode with respect to the silver / silver chloride reference electrode is the value of the polymerization voltage shown in Table 1.
  • a voltage was applied to the anode to perform electrolytic polymerization so as to form a solid electrolyte layer.
  • Solid Electrolytic Capacitor B2 A total of 20 solid electrolytic capacitors B2 were formed in the same manner as the solid electrolytic capacitor A5 except that electrolytic polymerization was performed by a two-pole method.
  • electrolytic polymerization the anode on which the precoat layer is formed and the Ti electrode as the counter electrode are immersed in the polymerization solution, and the potential of the anode with respect to the silver / silver chloride reference electrode is the value of the polymerization voltage shown in Table 1.
  • a voltage was applied to the anode to perform electrolytic polymerization so as to form a solid electrolyte layer.
  • the full half width of the first peak derived from polypyrrole or PEDOT is obtained, and the shift amount from the position (reference position) of the second peak is obtained.
  • the shift amount was evaluated by the ratio (%) of the actual shift amount (cm -1 ) from the reference position of the first peak when the wave number of the reference position was 100%.
  • an accelerated test was conducted by applying a rated voltage to the solid electrolytic capacitor for 2000 hours in an environment of 145 ° C. Then, in the same procedure as for the initial capacitance, the capacitance after the acceleration test was measured in an environment of 20 ° C., and the average value of 20 solid electrolytic capacitors was obtained. The value obtained by subtracting the initial capacitance from the capacitance after the acceleration test was used as the capacitance change rate, and was expressed as a ratio when the initial capacitance was 100%. The rate of change in capacitance is a negative value, and the smaller the value, the lower the heat resistance.
  • a solid electrolytic capacitor element and a solid electrolytic capacitor having excellent heat resistance are provided. Therefore, the solid electrolytic capacitor element and the solid electrolytic capacitor can be used in various applications where high reliability is required.
  • Solid electrolytic capacitor 2 Condenser element 3: Resin exterior body 4: Anode terminal 5: Cathode terminal, 6: Anode body, 7: Dielectric layer, 8: Cathode part, 9: Solid electrolyte layer, 10 : Cathode lead layer, 11: Carbon layer, 12: Metal paste layer, 13: Separation part, 14: Adhesive layer

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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WO2024203051A1 (ja) * 2023-03-27 2024-10-03 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ素子および固体電解コンデンサ

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US12354812B2 (en) * 2021-01-22 2025-07-08 Panasonic Intellectual Property Management Co., Ltd. Solid electrolytic capacitor element and solid electrolytic capacitor

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JPH1036667A (ja) * 1996-07-18 1998-02-10 Nitto Denko Corp 導電性ポリアニリン組成物及びこれを固体電解質とする固体電解コンデンサ
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US20230360859A1 (en) 2023-11-09

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