WO2023145644A1 - 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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WO2023145644A1
WO2023145644A1 PCT/JP2023/001712 JP2023001712W WO2023145644A1 WO 2023145644 A1 WO2023145644 A1 WO 2023145644A1 JP 2023001712 W JP2023001712 W JP 2023001712W WO 2023145644 A1 WO2023145644 A1 WO 2023145644A1
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electrolytic capacitor
solid electrolytic
polymer
solid electrolyte
anode foil
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French (fr)
Japanese (ja)
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昌利 竹下
真弓 前西
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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 CN202380018453.4A priority Critical patent/CN118591856A/zh
Priority to JP2023576873A priority patent/JPWO2023145644A1/ja
Priority to US18/833,094 priority patent/US20250118499A1/en
Publication of WO2023145644A1 publication Critical patent/WO2023145644A1/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
    • H01G9/15—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
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—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
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes

Definitions

  • 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 body 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, for example, an anode body, a dielectric layer formed on the surface of the anode body, and a cathode section covering at least part of the dielectric layer.
  • the cathode portion includes a conductive polymer (eg, a conjugated polymer and a dopant) covering at least a portion of the dielectric layer.
  • a conductive polymer is also referred to as a solid electrolyte.
  • a method of using a liquid dispersion containing a conjugated polymer and a dopant is often used to form a solid electrolyte.
  • Patent Document 1 discloses that an anode body having a dielectric film formed on its surface is impregnated with a first dispersion solution containing particles of a first conductive polymer and a first solvent, followed by a second and a second solvent, wherein the pH of the first dispersion solution is greater than the pH of the second dispersion solution 7, a method for manufacturing an electrolytic capacitor is proposed.
  • Patent Document 2 is composed of PEDOT (poly(3,4-ethylenedioxythiophene)) and a polyanion, and the peak intensity at 1260 cm -1 of the Raman spectrum is I 1 and the peak intensity at 1420 cm -1 is I 2 , and light absorption
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • a polyanion the peak intensity at 1260 cm -1 of the Raman spectrum is I 1 and the peak intensity at 1420 cm -1 is I 2 , and light absorption
  • the following formula (I): ⁇ (I 1 /I 2 )-0.135 ⁇ ( A 2 /A 1 ) ( 1) proposed a conductive polymer composite having a conductive potential ⁇ of -0.23 or more.
  • JP 2013-58807 A Japanese Patent Application Laid-Open No. 2021-134331
  • the surface layer of the anode body such as the anode foil is formed with a porous portion having fine voids.
  • the liquid dispersion contains a particulate conductive polymer in which a polymer dopant (such as a polymer anion) is combined with a conjugated polymer. Therefore, when a solid electrolyte is formed using a dispersion, it is difficult for the particulate conductive polymer to be filled deep into the fine voids, and it is difficult to increase the filling rate of the conductive polymer in the porous portion. In this case, repeated charging and discharging greatly reduces the capacity.
  • a first aspect of the present disclosure comprises: an anode foil containing an aluminum element and having a porous portion in at least a surface layer; a dielectric layer covering at least a portion of the surface of the anode foil; and at least a portion of the dielectric layer. a solid electrolyte covering, The solid electrolyte contains elemental sulfur, and in the anode foil having the dielectric layer, a first portion filled in the voids of the porous portion, and a main surface of the anode foil having the dielectric layer.
  • the abundance ratio of sulfur element is 0.5% or more when the abundance ratio of aluminum element is 100% in element mapping using an electron probe microanalyzer of the cross section of the porous part .
  • a second aspect of the present disclosure relates to a solid electrolytic capacitor including at least one of the solid electrolytic capacitor elements described above.
  • FIG. 1 is a cross-sectional schematic diagram of a solid electrolytic capacitor according to an embodiment of the present disclosure
  • liquid dispersions include particulate conductive polymers (such as conjugated polymers and dopants) of relatively high molecular weight.
  • high-molecular-weight polymer anions are preferably used as dopants because they have a high affinity for conjugated polymers and tend to ensure high stability and high heat resistance.
  • the action of moisture or oxygen contained in the air causes the conjugated polymer to oxidize and deteriorate, and the dopant to de-dope due to decomposition, etc., resulting in deterioration of the conductive polymer.
  • the conductivity of the conductive polymer decreases.
  • the dopant is adsorbed to the conjugated polymer during charging, and the dopant is desorbed from the conjugated polymer during discharging. happenss repeatedly. The movement of the first portion held in the void is restricted by the metal framework of the porous portion, whereas the second portion is likely to move according to the volume change due to repeated charging and discharging. Distortion is likely to occur between the two parts.
  • Such distortion causes cracks between the surface of the first portion or porous portion and the second portion, resulting in less contact. This is believed to increase the resistance between the first portion or porous portion and the second portion. As a result, when charging and discharging are repeated, it becomes difficult to extract the capacity, and the capacity is considered to decrease.
  • the solid electrolytic capacitor element of the present disclosure includes an anode foil containing an aluminum element and having a porous portion at least on the surface layer, a dielectric layer covering at least a part of the surface of the anode foil, and the a solid electrolyte covering at least a portion of the dielectric layer.
  • the solid electrolyte contains elemental sulfur, and in the anode foil having the dielectric layer, a first portion filled in the voids of the porous portion, and a main surface of the anode foil having the dielectric layer. and a second portion that protrudes from.
  • the abundance ratio of sulfur element is 0.5% or more when the abundance ratio of aluminum element is 100%.
  • the first portion may include a first polymer component corresponding to a conjugated polymer and a second polymer component corresponding to a polymer anion containing a sulfur element.
  • the first polymer component may contain elemental sulfur.
  • a second peak characteristic of the second polymer component having an intensity I p1 of the first peak characteristic of the first polymer component to the intensity I p2 : I p1 /I p2 may be 2 or more.
  • the ratio I p1 /I p2 may be 7 or less.
  • the conjugated polymer may contain a monomer unit corresponding to a thiophene compound.
  • the polymeric anion may comprise monomeric units corresponding to aromatic sulfonic acid compounds.
  • the first peak may be observed in a range from 1200 cm ⁇ 1 to 1600 cm ⁇ 1 .
  • the second peak may be observed in a range from 800 cm ⁇ 1 to 1100 cm ⁇ 1 .
  • the polymer anion may have a weight average molecular weight of 100 or more and 500,000 or less.
  • a solid electrolytic capacitor of the present disclosure includes at least one solid electrolytic capacitor element according to any one of (1) to (7) above.
  • the solid electrolytic capacitor may include a plurality of stacked solid electrolytic capacitor elements.
  • the solid electrolyte contains a sulfur (S) element and is filled in the voids of the porous portion (such as the above recesses) in the anode foil having the dielectric layer. and a second portion protruding from the main surface of the anode foil having the dielectric layer.
  • the anode foil contains an aluminum (Al) element.
  • the abundance ratio of the S element is 0.5% or more when the abundance ratio of the Al element is 100%.
  • the solid electrolytic capacitor element may be simply referred to as a capacitor element.
  • the abundance ratio of the S element is relatively large at 0.5% or more with respect to the abundance ratio of the Al element in the porous portion, so that the decrease in capacity when charging and discharging are repeated can be suppressed.
  • the S element is mainly derived from the conjugated polymer and dopant that constitute the solid electrolyte.
  • a polythiophene-based conjugated polymer contains an S element in a thiophene ring, and a dopant contains an S element derived from an anionic group such as a sulfo group.
  • the anode foil containing Al element is mainly composed of Al or Al alloy, and the dielectric layer is composed of Al oxide.
  • the ratio of the solid electrolyte contained in the porous portion is relatively increased (in other words, the ratio of the solid electrolyte contained in the porous portion is increased. This means that the filling rate of the solid electrolyte in the voids of the solid portion increases).
  • the content ratio of the S element in the porous portion is within the above range, so that a relatively high filling rate of the solid electrolyte is obtained, and the number of air flow paths is reduced, so that the deterioration of the solid electrolyte progresses. is considered to be hindered.
  • the relatively high content of S element in the porous portion as described above can be obtained, for example, by forming a dielectric layer on the surface of an anode foil containing Al element and having a porous portion on at least the surface layer. It is obtained by immersing the anode foil on the surface in a polymerization solution containing a conjugated polymer precursor and an S element-containing polymer anion, and performing electrolytic polymerization at a relatively low polymerization potential in a three-electrode system.
  • the polymerization of the conjugated polymer precursor gradually progresses in the presence of the polymer anion, which is relatively stable as a dopant, and the conjugated polymer and the polymer It is thought that a conductive polymer interacting with an anion is generated and a dense solid electrolyte is formed. Since the precursor and the polymer anion are in a dissolved state in the polymerization liquid, they easily penetrate deep into the fine voids of the porous portion. Therefore, polymerization is likely to proceed not only near the opening of the voids, but also deep within the voids. Therefore, it is considered that a high filling rate of the solid electrolyte in the voids can be obtained.
  • the polymerization of the precursor of the conjugated polymer proceeds while interacting with the polymer anion.
  • Anions are dispersed relatively uniformly, and a relatively high doping rate can be easily obtained. Therefore, high conductivity of the solid electrolyte in the first portion can be obtained, and dedoping or deterioration of the conjugated polymer is less likely to occur even if charging and discharging are repeated.
  • the filling rate of the solid electrolyte in the porous portion is high, the contact between the first portion or the porous portion and the second portion is maintained even if the volume of the solid electrolyte is repeatedly changed due to repeated charging and discharging. Therefore, it is considered that the excellent effects as described above can be obtained.
  • the porous part Even when the first part is formed using a liquid dispersion containing a conjugated polymer containing an S element such as PEDOT and a polymer anion containing an S element such as polystyrene sulfonic acid (PSS), the porous part
  • the abundance ratio of the S element is low, for example, less than 0.5%. This is probably because, as described above, the filling rate of the solid electrolyte in the porous portion is low even when the liquid dispersion is used.
  • Three-electrode electropolymerization is performed using three electrodes: an anode foil with a dielectric layer formed on its surface, a counter electrode, and a reference electrode.
  • a reference electrode enables precise control of 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, which utilizes an anode foil and a counter electrode.
  • the orientation of the formed conjugated polymer increases, the dispersibility of the polymer anion increases, and a more uniform and denser solid electrolyte is formed at a high filling rate in the pores of the porous portion. Conceivable.
  • a relatively high doping rate can be easily obtained by highly dispersing the polymer anion, and the conductivity itself of the solid electrolyte can be easily increased.
  • the abundance ratio of the S element in the porous portion is 0.5% or more (e.g., 0.50% or more), may be 0.65% or more, or is 0.7% or more (e.g., 0.70% % or more).
  • the porous portion is highly filled with a highly conductive solid electrolyte, so deterioration of the solid electrolyte is suppressed when charging and discharging are repeated, and the first portion Alternatively, the contact between the porous portion and the second portion can be maintained, thereby suppressing a decrease in capacity.
  • the resistance of the first portion can be kept low from the initial stage, the initial equivalent series resistance (ESR) can be kept low, and a relatively high initial capacitance can be ensured.
  • ESR initial equivalent series resistance
  • the abundance ratio of the S element is, for example, 5% or less.
  • Electrode Micro Analyzer Electro Probe Micro Analyzer: EPMA
  • EMA Electro Probe Micro Analyzer
  • the area from the main surface of the anode foil to the bottom of the porous portion and having a width of 5 ⁇ m is subjected to element mapping from the difference in the wavelength of characteristic X-rays by EPMA, and the Net intensity of the contained elements is measured.
  • Net intensity is a value obtained by subtracting the background (noise) from the measured value of each element.
  • the ratio (%) of the net intensity of the S element to the net intensity of the Al element as 100% is obtained.
  • the ratio (%) of the net intensity of the S element is obtained, the average value is calculated, and the ratio of the S element when the abundance ratio of the Al element in the porous portion is 100% The abundance ratio (%).
  • the conditions for the EPMA analysis are as follows. Environment during measurement: 25°C, atmospheric pressure Acceleration voltage: 15.0 kV Beam current: 20.1nA Integration time: 180.0ms/point (12 minutes mode) Analysis crystal: AP/CH1, PbST/CH2, PET/CH3, LiF/CH4, LSA80/CH5
  • a sample for analysis can be prepared, for example, by the following procedure. First, a solid electrolytic capacitor is embedded in a hardening resin, and the hardening resin is hardened.
  • the anode foil has a first end and a second end opposite to the first end, and the solid electrolyte is formed in a portion of the anode foil on the second end side.
  • the cured product obtained above is wet-polished or dry-polished so that the is exposed.
  • the exposed cross section is smoothed by ion milling.
  • a platinum film having a thickness of 1 nm to 2 nm is formed on the smoothed cross section by sputtering platinum (Pt) using a sputtering apparatus. A sample is thus obtained for analysis.
  • the cross section is 0 from the end of the region in which the solid electrolyte is formed on the second end side. Let the cross section be at the position of ⁇ 0.05.
  • Capacitor element (anode foil)
  • the anode foil included in the capacitor element contains Al element.
  • Al functions as a valve action metal.
  • the anode foil may contain Al metal, may contain Al alloy, or may contain both.
  • the anode foil has a porous portion on at least the surface layer.
  • the porous portion contains many fine voids.
  • the porous portion increases the surface area and provides high capacity.
  • the porous portion can be formed, for example, by roughening the surface of a metal foil containing Al element.
  • the anode foil may have, for example, a core and porous portions formed on both surfaces of the core and continuous with the core.
  • the porous portion is the roughened outer portion of the metal foil, and the remainder, which is the inner portion of the metal foil, is the core portion.
  • the porous portion may be formed on a part of the surface layer of the anode foil, or may be formed on the entire surface layer.
  • the surface roughening can be performed by an etching process or the like.
  • the etching treatment may be performed by electrolytic etching or by chemical etching.
  • the thickness of the porous portion, the shape and size of the voids, etc. are adjusted by the etching conditions (the number of etching steps and time, the current density, the composition and temperature of the etchant, etc.). good too.
  • the thickness of the porous portion may be appropriately selected depending on the application of the solid electrolytic capacitor, the required performance, and so on.
  • the thickness of the porous portion may be, for example, 1/10 or more and 4/10 or less, or 2/10 or more and 4/10 or less of the thickness of the anode foil per one side of the anode foil.
  • the cathode part is formed through a dielectric at the second end side portion of the anode foil.
  • a portion of the anode foil on the second end side where the cathode portion is formed is sometimes called a cathode forming portion.
  • the anode foil has, for example, a porous portion at least on the surface layer of the cathode forming portion.
  • a portion of the anode foil on the first end side where the cathode portion is not formed is sometimes called an anode lead portion.
  • An anode lead terminal may be connected to the anode lead-out portion.
  • the dielectric layer is formed to cover at least part of the surface of the anode foil.
  • a dielectric layer is an insulating layer that functions as a dielectric.
  • the dielectric layer is formed by anodizing Al on the surface of the anode foil by chemical conversion treatment or the like.
  • the surface of the dielectric layer has fine unevenness according to the shape of the surface of the porous portion.
  • the dielectric layer may be formed of a material that functions as a dielectric layer.
  • the dielectric layer includes, for example, oxides of valve metals as such materials. Since the anode foil contains Al element, the dielectric layer formed by chemical conversion usually contains Al 2 O 3 . However, the dielectric layer is not limited to these specific examples.
  • the cathode section includes at least a solid electrolyte covering at least a portion of the dielectric layer.
  • the solid electrolyte is formed through the dielectric layer in the portion of the anode foil on the second end side.
  • the cathode part usually includes a solid electrolyte that covers at least part of the dielectric layer, and a cathode extraction layer that covers at least part of the solid electrolyte. The solid electrolyte and the cathode extraction layer are described below.
  • the solid electrolyte contains S element.
  • the solid electrolyte has a first portion filled in the voids of the porous portion and a second portion protruding from the main surface of the anode foil having the dielectric layer.
  • the solid electrolyte is composed of a conductive polymer.
  • a conductive polymer includes a conjugated polymer and a dopant.
  • the solid electrolyte may further contain additives as needed.
  • the S element contained in the solid electrolyte is mainly derived from the conductive polymer. More specifically, the S element is contained at least in the dopant, and may be contained in both the dopant and the conjugated polymer. Also, the S element is contained in at least the first portion, and usually contained in both the first portion and the second portion.
  • At least the first portion of the solid electrolyte is formed by triode electropolymerization as described above.
  • the first portion may include a first polymer component corresponding to the conjugated polymer and a second polymer component corresponding to the polymer anion containing the S element.
  • Conjugated polymers corresponding to the first polymer component include known conjugated polymers used in solid electrolytic capacitors, such as ⁇ -conjugated polymers.
  • 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.
  • polythiophenes include PEDOT (poly(3,4-ethylenedioxythiophene)) and the like.
  • the first polymer component may contain the S element.
  • a conjugated polymer constituting such a first polymer component includes, for example, a monomer unit corresponding to a thiophene compound.
  • the use of a thiophene compound as a precursor facilitates the progress of electrolytic polymerization even in the presence of polymer anions containing the S element by adjusting the conditions of the electrolytic polymerization, which is more advantageous in increasing the abundance ratio of the S element.
  • Thiophene compounds include compounds having a thiophene ring and capable of forming a repeating structure of corresponding monomer units. Thiophene compounds can be linked at the 2- and 5-positions of the thiophene ring to form a repeating structure of monomeric units.
  • 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 the thiophene ring.
  • 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.
  • 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 such as PEDOT containing at least a monomer unit corresponding to a 3,4-ethylenedioxythiophene compound (such as 3,4-ethylenedioxythiophene (EDOT)) may be used.
  • 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 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.
  • the first part may contain, as a dopant, a second polymer component corresponding to a polymer anion containing the S element.
  • a second polymer component corresponding to a polymer anion containing the S element.
  • polymer anions constituting the second polymer component include polymers having a plurality of sulfo groups.
  • the polymeric anion may have other anionic groups (eg, carboxy groups) in addition to the sulfo groups.
  • the anionic group (sulfo group, carboxy group, etc.) of the dopant may be contained in a free form, an anion form, or a salt form, and may be bound or interacted with the conjugated polymer. may be included in In the present specification, all these forms are sometimes simply referred to as "anionic group", “sulfo group”, or "carboxy group”.
  • Polymer anions having a sulfo group include, for example, polymer-type polysulfonic acids.
  • Specific examples of polymer anions include polyvinylsulfonic acid, polystyrenesulfonic acid (including copolymers and substituents having substituents), polyarylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly(2- acrylamide-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyester sulfonic acid (such as aromatic polyester sulfonic acid), and phenolsulfonic acid novolac resin.
  • the polymer anion is not limited to these specific examples.
  • the solid electrolyte may contain one type of polymer anion, or may contain two or more types in combination.
  • the Mw of the polymer anion is, for example, 100 or more and 500,000 or less. From the viewpoint of facilitating high filling of the conductive polymer into the voids of the porous portion, the Mw of the polymer anion constituting at least the first portion is preferably 100,000 or less, and is 1,000 or more and 100,000 or less, or 10,000 or more and 100,000 or less. is more preferred. Further, when the Mw of the polymer anion is within such a range, it is easy to obtain higher dispersibility and a relatively high doping rate of the polymer anion in the first part, which is advantageous in ensuring higher conductivity. . In addition, high stability of dopant and conductive polymer is likely to be obtained.
  • the amount of the dopant contained in the solid electrolyte is, for example, 10 parts by mass or more and 1000 parts by mass or less, and 20 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the conjugated polymer. good too. It may be 50 parts by mass or more and 200 parts by mass or less from the viewpoint of easily obtaining higher dispersibility of the polymer anion and a relatively high doping rate.
  • the capacitor element of the present disclosure at least a first peak specific to the first polymer component (conjugated polymer) and a second peak specific to the second polymer component are observed in the Raman spectrum of the first portion.
  • the main component of the solid electrolyte is a conjugated polymer, and in the Raman spectrum of the solid electrolyte, the peak (first peak) attributed to the CC stretching vibration derived from the conjugated polymer is the highest and characteristic. be.
  • the solid electrolyte exhibits high crystallinity due to the high orientation of the conjugated polymer.
  • the conjugated polymer is in an energetically stabilized state. Therefore, the first part shows a characteristic Raman spectrum in which the first and second peaks as described above are observed.
  • the Raman spectrum of the first portion is 1200 cm ⁇ 1
  • a first peak is observed in the range from 800 cm ⁇ 1 to 1100 cm ⁇ 1
  • a second peak is observed in the range from 800 cm ⁇ 1 to 1100 cm ⁇ 1 .
  • the first peak is assigned to the CC stretching vibration of the thiophene ring in the monomer unit corresponding to the thiophene compound.
  • the second peak is attributed to CS stretching vibration between the aromatic ring and the S element of the sulfo group in the monomer unit corresponding to the aromatic sulfonic acid compound.
  • the position of the first peak is, for example, 1400 cm -1 or more and 1450 cm -1 or less, and 1410 cm -1 or more and 1435 cm -1 or less. good too.
  • the polymer anion contains at least polystyrene sulfonic acid
  • the position of the second peak is, for example, 900 cm ⁇ 1 or more and 1050 cm ⁇ 1 or less, and may be 950 cm ⁇ 1 or more and 1050 cm ⁇ 1 .
  • the Raman spectrum of the first part of the solid electrolyte formed using the liquid dispersion does not show such characteristic peaks. This is probably because the observation of Raman scattered light is inhibited by fluorescence emission.
  • polymerization proceeds in the liquid phase, so it is thought that the conductive polymer particles obtained tend to segregate high-molecular-weight polymer anions on the surface compared to conjugated polymer precursors. be done.
  • the conductive polymer particles with polymer anions segregated on the surface are filled in the porous part, so in the Raman spectrum of the first part, the fluorescence emission due to the segregated polymer anions is as described above. It is considered that no characteristic peak is observed.
  • the intensity Ip1 of the first peak characteristic of the first polymer component (conjugated polymer) and the second peak characteristic of the second polymer component (polymer anion) may be 2 or more, 3 or more, or 4 or more.
  • the orientation and crystallinity of the conjugated polymer in the first portion are relatively high. Therefore, it is easy to ensure high conductivity of the solid electrolyte of the first portion.
  • the I p1 /I p2 ratio may be 5 or more or 5.5 or more.
  • the I p1 /I p2 ratio is, for example, 10 or less.
  • the I p1 /I p2 ratio is preferably 7 or less from the viewpoint of easily ensuring higher conductivity by obtaining a relatively high doping rate.
  • the I p1 /I p2 ratio is, for example, 2 or more and 10 or less (or 7 or less), and may be 4 or more and 10 or less (or 7 or less). In these numerical ranges, the lower limits may be replaced with the above values.
  • the intensity of each peak corresponds to the peak height obtained by subtracting the background height from the height of each peak.
  • the Raman spectrum of the solid electrolyte of the first part is measured under the following conditions for the solid electrolyte present in the cross section of the porous portion at the predetermined position of the solid electrolytic capacitor element.
  • 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. For example, when the conjugated polymer is PEDOT, the irradiation laser light wavelength is 784.73 nm, the laser power density is 870 W/cm 2 , and the exposure time is 60 seconds.
  • a sample collected by the following procedure can be used for Raman spectrum measurement.
  • a solid electrolytic capacitor is embedded in a hardening resin, and the hardening resin is hardened.
  • a cross-section perpendicular to the length direction and parallel to the thickness direction of the capacitor element is exposed by subjecting the cured product to polishing or cross-section polishing.
  • the cross section is the end of the region in which the solid electrolyte is formed opposite to the anode lead-out portion (the second end). It is a cross section at a position of 0 to 0.05 from the end on the second end side).
  • a Raman spectrum is measured for an 8 ⁇ m ⁇ 8 ⁇ m region of the solid electrolyte (first portion) formed in the pits on the surface of the porous portion in the exposed cross section of the sample.
  • the intensities of the first peak and the second peak are obtained by averaging the measured values for twelve 8 ⁇ m ⁇ 8 ⁇ m regions of the first portion formed in the pits of the porous portion.
  • At least the first portion of the solid electrolyte can be formed by subjecting a conjugated polymer precursor to triode electropolymerization in the presence of a dopant on the surface of the dielectric layer.
  • electrolytic polymerization is performed while the cathode forming portion of the anode foil having the dielectric layer formed thereon is immersed in a liquid composition (polymerization solution) containing a conjugated polymer precursor and a dopant.
  • the dopant can be doped at a relatively high doping rate, so that high conductivity of the solid electrolyte can be ensured and the conjugated polymer can be stabilized in terms of energy. Therefore, deterioration of the solid electrolyte can be suppressed, high conductivity can be maintained even after repeated charging and discharging, and high capacity can be secured.
  • 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).
  • liquid composition When using other conductive materials, additives, etc., they may be added to the liquid composition.
  • the liquid composition may optionally contain an oxidizing agent.
  • the oxidizing agent may be applied to the anode foil before or after the liquid composition is brought into contact with the anode foil 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 may be used singly or in combination of two or more.
  • Three-electrode electropolymerization is performed in a state in which the anode foil, 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 foil is, for example, 0.6 V or more and 1.5 V or less.
  • the polymerization voltage is preferably more than 0.9 V and 1.2 V or less (or 1.1 V or less) from the viewpoint of facilitating high filling in the voids of the porous portion and facilitating securing of relatively high crystallinity of the solid electrolyte. , 1 V or higher (eg, 1.0 V or higher) and 1.2 V or lower, or 1 V or higher (eg, 1.0 V or higher) and 1.1 V or lower.
  • the polymerization voltage is the potential of the anode foil with respect to the reference electrode (silver/silver chloride electrode (Ag/Ag + )).
  • a power supply such as a power supply tape
  • the potential of the anode foil is the potential of a feeder electrically connected to the anode foil.
  • 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.
  • the precoat layer may be formed using a liquid dispersion containing a conductive polymer (conjugated polymer, dopant, etc.).
  • the liquid dispersion used for forming the precoat layer has a smaller particle size of the conductive polymer and a lower concentration than the liquid dispersion used for forming the solid electrolyte constituting the cathode part.
  • the average primary particle size of the conductive polymer particles contained in the liquid dispersion for the precoat layer is, for example, 100 nm or less, and may be 60 nm or less.
  • the dry solid content concentration of the liquid dispersion is, for example, 1.2% by mass or less.
  • the average primary particle diameter of the conductive polymer particles is usually 200 nm or more, and the dry solid content concentration is 2% by mass. That's it.
  • 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 first portion is formed by electrolytic polymerization, even if the precoat layer is formed using a liquid dispersion, the polymerization liquid can be sufficiently penetrated into fine voids, and the first portion can be obtained at a high filling rate. It can form one part.
  • Part 2 The second part may differ from the first part in at least one of the solid electrolyte composition and film quality, or may be the same in both composition and film quality.
  • the first portion may be the first layer and the second portion may be the second layer.
  • at least one of composition and film quality may be different between the first layer and the second layer, or both the composition and film quality may be the same.
  • the second portion may be composed of a plurality of layers. At least two of the plurality of layers may differ in at least one of composition and film quality, or both may be the same.
  • the solid electrolyte of the second part may be formed by chemical polymerization, general bipolar electropolymerization, or liquid dispersion, but the dopant is highly dispersed throughout the solid electrolyte to ensure high conductivity. From the viewpoint of facilitating the formation of the solid electrolyte and suppressing deterioration of the solid electrolyte, it is preferable that the second portion is also formed by three-electrode electrolytic polymerization.
  • the conjugated polymer contained in the second portion may be selected from, for example, the conjugated polymers described for the first portion.
  • the Mw of the conjugated polymer may be selected from the range described for the first portion.
  • the dopant at least one selected from the group consisting of the polymer anions and anions described for the first portion may be used. Examples of 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. It is preferable to use a polymer anion from the viewpoint of easily obtaining higher stability.
  • the amount of the dopant contained in the solid electrolyte is, for example, 10 parts by mass or more and 1000 parts by mass or less, 20 parts by mass or more and 500 parts by mass or less, or 50 parts by mass with respect to 100 parts by mass of the conjugated polymer. It may be more than or equal to 200 parts by mass or less.
  • the second part may be formed using a liquid dispersion (or solution) containing a conjugated polymer and a dopant.
  • the second portion When forming the second portion by electropolymerization, the second portion may be formed in the same manner as described for the first portion.
  • the polymerization voltage of the electropolymerization may be in the range described for the first part, may be 0.6 V or more and 1.5 V or less, or may be 0.7 V or more and 1.2 V or less.
  • Each of the first portion and the second portion may further contain at least one selected from the group consisting of known additives and known conductive materials other than conductive polymers, if necessary.
  • the conductive material include at least one selected from the group consisting of conductive inorganic materials such as manganese dioxide, and TCNQ complex salts.
  • Additives include known additives added to solid electrolytes (eg, coupling agents, silane compounds), known conductive materials other than conductive polymers, and water-soluble polymers.
  • Each of the first portion and the second portion may contain one kind of these additives or a combination of two or more kinds thereof.
  • the additive contained in each layer may be the same or different.
  • Each of the first portion and the second portion may be a single layer or may be composed of multiple layers.
  • the types, compositions, contents, etc. of the conductive polymers and additives contained in each layer may be the same or different.
  • a layer that enhances adhesion may be interposed between the dielectric layer and the solid electrolyte.
  • the cathode extraction layer may include at least a first layer that is in contact with the solid electrolyte and covers at least a portion of the solid electrolyte, and may include a first layer and a second layer that covers the first layer.
  • 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.
  • a solid electrolytic capacitor includes at least one capacitor element.
  • the solid electrolytic capacitor may be of wound type, chip type or laminated type.
  • a solid electrolytic capacitor may include two or more stacked capacitor elements.
  • the solid electrolytic capacitor may include two or more wound capacitor elements.
  • the configuration of the capacitor element may be selected according to the type of solid electrolytic capacitor.
  • one end of the cathode lead terminal is electrically connected to the cathode extraction layer.
  • the cathode lead terminal is, for example, applied to the cathode lead layer with a conductive adhesive and joined to the cathode lead layer via the conductive adhesive.
  • One end of the anode lead terminal is electrically connected to the anode foil.
  • the other end of the anode lead terminal and the other end of the cathode lead terminal are pulled out from the resin outer package 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 anode lead terminal and the cathode lead 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 lead terminal and the cathode lead terminal is located on the opening side of the bottomed case, and the opening of the bottomed case is sealed with the sealing body. By doing so, a solid electrolytic capacitor may be formed.
  • 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 , and an anode lead terminal 4 at least a part of which is exposed outside the resin sheathing body 3 . and a cathode lead terminal 5 .
  • the anode lead terminal 4 and the cathode lead terminal 5 can be made of metal such as copper or 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.
  • the capacitor element 2 includes an anode foil 6 made of Al foil, a dielectric layer 7 covering the anode foil 6 , and a cathode section 8 covering the 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 anode foil 6 has porous portions formed by etching or the like on both surface layers.
  • the solid electrolyte layer 9 contains the S element, and in the anode foil 6 having the dielectric layer 7, a first portion filled in the voids of the porous portion and a second portion protruding from the main surface of the anode foil. have.
  • the abundance ratio of sulfur element is 0.5% or more when the abundance ratio of Al element in the porous portion is 100%.
  • the anode foil 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 foil 6 in a strip shape, so that the cathode portion 8 and the anode are separated from each other. Contact with the foil 6 is restricted.
  • the other part of the region of the anode foil 6 that does not face the cathode portion 8 is electrically connected to the anode lead terminal 4 by welding.
  • the cathode lead terminal 5 is electrically connected to the cathode portion 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 foil 6 was produced by roughening both surfaces of an aluminum foil (thickness: 130 ⁇ m) by etching. The thickness of the porous portions formed on both surface layers of the anode foil was 50 ⁇ m.
  • a voltage was applied to the anode foil 6 so that the potential of the anode foil 6 (more specifically, the electric power feeder attached to the anode lead-out portion) with respect to the reference electrode became the value of the superposition voltage shown in Table 1, and the temperature was kept at 25°C. to form a solid electrolyte layer 9.
  • a silver paste containing silver particles and a binder resin (epoxy resin) is applied to the surface of the first layer 11 and heated at 150 to 200° C. for 10 to 60 minutes to cure the binder resin, forming a second layer.
  • (Metal paste layer) 12 was formed.
  • the cathode lead layer 10 composed of the first layer (carbon layer) 11 and the second layer (metal paste layer) 12 is formed, and the cathode portion 8 composed of the solid electrolyte layer 9 and the cathode lead layer 10 is formed.
  • Capacitor element 2 was produced as described above.
  • Solid electrolytic capacitor B1>> A solid electrolyte layer 9 was formed by the following procedure. Other than this, a solid electrolytic capacitor was produced in the same manner as in the solid electrolytic capacitor A1.
  • the anode foil 6 having the dielectric layer 7 was immersed in a liquid dispersion containing a conductive polymer and dried at 120°C for 10 to 30 minutes.
  • the solid electrolyte layer 9 was formed by repeating the immersion in the liquid dispersion and the drying four times each.
  • an aqueous dispersion ( The average particle size of the conductive polymer in the dispersion: 400 nm to 600 nm) was used.
  • Capacitance change rate (C 1 -C 0 )/C 0 ⁇ 100 (%) The capacitance change rate is a negative value, indicating that the smaller the value, the lower the capacity after repeated charging and discharging.
  • Table 1 shows the evaluation results.
  • A1 to A3 are examples, and B1 is a comparative example.
  • the initial capacitance C0 and the initial ESR are shown as relative values when the value of B1 is 100.
  • A1 to A3 obtained high initial capacity and low ESR as described above, and obtained an appropriate I p1 /I p2 ratio in the Raman spectrum. It is considered that high conductivity is ensured. This is probably because in the first portion, a relatively high doping rate is obtained, and the conjugated polymer is formed with a high degree of orientation, resulting in a high degree of crystallinity.
  • the present disclosure it is possible to suppress a decrease in capacity when the solid electrolytic capacitor is repeatedly charged and discharged.
  • INDUSTRIAL APPLICABILITY The solid electrolytic capacitor element and the solid electrolytic capacitor of the present disclosure stably provide a high capacity even after repeated charging and discharging, and therefore can be used in various applications that require reliability or long life.
  • the uses of the solid electrolytic capacitor element and the solid electrolytic capacitor are not limited to these.
  • Solid electrolytic capacitor 2 Capacitor element 3: Resin sheath 4: Anode lead terminal 5: Cathode lead terminal 6: Anode foil 7: Dielectric layer 8: Cathode part 9: Solid electrolyte layer 10: Cathode extraction layer 11: Third 1 layer (carbon layer) 12: Second layer (metal paste layer) 13: Separation part 14: Adhesive layer

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WO2024111506A1 (ja) * 2022-11-25 2024-05-30 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ
WO2025177956A1 (ja) * 2024-02-20 2025-08-28 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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JP2011029580A (ja) * 2009-06-30 2011-02-10 Japan Carlit Co Ltd:The 固体電解コンデンサおよびその製造方法
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