WO2006068302A1 - Element de condensateur a electrolyte liquide, condensateur a electrolyte liquide et leur procede de fabrication - Google Patents

Element de condensateur a electrolyte liquide, condensateur a electrolyte liquide et leur procede de fabrication Download PDF

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Publication number
WO2006068302A1
WO2006068302A1 PCT/JP2005/024155 JP2005024155W WO2006068302A1 WO 2006068302 A1 WO2006068302 A1 WO 2006068302A1 JP 2005024155 W JP2005024155 W JP 2005024155W WO 2006068302 A1 WO2006068302 A1 WO 2006068302A1
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Prior art keywords
electrolytic capacitor
solid electrolytic
capacitor element
conductor
dopant
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PCT/JP2005/024155
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English (en)
Japanese (ja)
Inventor
Kazumi Naito
Katutoshi Tamura
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Showa Denko K.K.
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Publication of WO2006068302A1 publication Critical patent/WO2006068302A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • 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
    • 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
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • the present invention relates to a method for manufacturing a solid electrolytic capacitor element having a low equivalent series resistance (ESR) value and a high capacity.
  • ESR equivalent series resistance
  • Aluminum capacitors and tantalum solid electrolytic capacitors are known as high-capacitance and low-ESR capacitors used in various electronic devices.
  • the solid electrolytic capacitor was formed on the surface layer of an aluminum foil having fine pores on the surface layer and a sintered body of tantalum powder having fine pores inside as one electrode (conductor). It is produced by sealing a solid electrolytic capacitor element composed of a dielectric layer and the other electrode (usually a semiconductor layer) provided on the dielectric layer and an electrode layer laminated on the other electrode. ing.
  • an organic compound or an inorganic compound is used, but a conductive polymer is preferably used in consideration of the heat resistance and low ESR characteristics of the produced capacitor.
  • This conductive polymer is a polymer having a high conductivity of 10 to 2 to 10 3 S ⁇ cm, and a polymer having a planar conjugated double bond (usually an insulator) High conductivity is exhibited by adding an electron donating compound called a dopant to a polymer having extremely low conductivity.
  • a single molecule (monomer) that can become a conductive polymer in the pores of a conductor is used in the presence of a dopant, or an appropriate oxidizing agent or The method of superposing
  • a dopant is taken in to obtain a conductive polymer.
  • Patent No. 1 9 4 5 3 5 8 and Patent No. 2 8 1 1 6 4 8 a semiconductor is formed by laminating an electropolymerization layer by an energization method after forming a chemical polymerization layer using an oxidizing agent. A method of forming a layer is described. Disclosure of the invention
  • an object of the present invention is to provide a method for producing a high-capacity solid electrolytic capacitor having a good ESR value.
  • the present inventors have supplied a sufficient amount of dopant to the conductor by forming a semiconductor layer by a current application method on the conductor impregnated with the dopant after forming the dielectric layer.
  • the semiconductor layer can be formed to a desired level, and it has been found that a high-capacity solid electrolytic capacitor element exhibiting a lower ESR value can be obtained, thereby completing the present invention. That is, the present invention provides the following method for producing a solid electrolytic capacitor element and a solid electrolytic capacitor produced using the method.
  • a method for manufacturing a solid electrolytic capacitor element in which a semiconductor layer containing a conductive polymer is formed on a conductor having a dielectric layer on the surface, the conductor having a dielectric layer on the surface is impregnated with a dopant, A method for producing a solid electrolytic capacitor element, characterized in that a semiconductor layer is formed by an energization method. 2. dopant, the manufacture of the solid electrolytic capacitor element of the 1, wherein electric conductivity of an electron-donating compound providing 10 one 1 ⁇ 1 0 3 S ⁇ cm one first conductive polymer upon doping during electropolymerization Method.
  • the semiconductor layer has the following general formula (1) or (2)
  • a solid electrolytic capacitor element according to 1 above which is at least one layer selected from a semiconductor mainly composed of a conductive polymer in which a dopant is added to a polymer containing a repeating unit represented by formula (1).
  • a polymer containing a repeating unit represented by the general formula (1) is represented by the following general formula (3)
  • each of 16 and 17 is independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or an alkyl group thereof. And a substituent which forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen atoms and is substituted with the cyclic structure. Those having a good vinylene bond and those having a phenylene structure which may be substituted are also included.
  • the conductive polymer is described in 5 above, wherein the conductive polymer is selected from polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof. Manufacturing method of the solid electrolytic capacitor element.
  • Semiconductors conductivity is 1 0 2-1 0 3 manufacturing method of a solid electrolytic capacitor element of the mounting serial in S ⁇ cm- the 5 1 by weight.
  • a solid electrolytic capacitor element obtained by the production method according to any one of 1 to 9 above.
  • the present invention provides a method for producing a solid electrolytic capacitor element in which a conductor layer impregnated with a dopant after formation of a dielectric layer is formed by a current application method, and a solid electrolytic capacitor in which the capacitor element obtained by the method is sealed Therefore, according to the present invention, a solid electrolytic capacitor having a low initial ESR value and a high capacity can be produced.
  • a method for producing a solid electrolytic capacitor element of the present invention and one embodiment of a solid electrolytic capacitor using the solid electrolytic capacitor element will be described.
  • Examples of the conductor used in the present invention include a metal containing at least one selected from tantalum, niobium, titanium and aluminum as a main component (a component of 50% by mass or more), niobium monoxide, or a mixture thereof. Is mentioned.
  • the metal may be an alloy.
  • a part of the metal may be used after at least one treatment selected from carbonization, phosphation, boronation, nitridation, and sulfidation.
  • the shape of the conductor is not particularly limited, and may be a foil shape, a plate shape, or a rod shape.
  • the conductor is obtained by molding a powdered conductor material or sintering after molding. You may sinter by attaching a powdery conductor to a part of foil-like or plate-like metal.
  • the surface of the conductor may be processed by etching or the like to have fine pores. In the molded body or the sintered body, fine pores can be provided inside the molded or sintered body by appropriately selecting the pressure during molding.
  • the lead can be directly connected to the conductor.
  • the conductor is a molded or sintered body, a part of the lead wire (or lead foil) prepared separately at the time of molding together with the conductor.
  • the part outside the molded lead wire (or lead foil) can be used as a lead for one electrode of the solid electrolytic capacitor element.
  • a semiconductor layer is not formed on a part of the conductor and left as an anode part. You can also.
  • An insulating resin may be adhered and cured in a headband shape at the boundary between the anode part and the semiconductor layer forming part in order to prevent the semiconductor layer from creeping up.
  • the conductor of the present invention include tantalum powder, niobium powder, alloy powder containing tantalum as a main component, alloy powder containing niobium as a main component, powder such as niobium monoxide powder, and the like.
  • examples thereof include a sintered body having a large number of pores and an aluminum foil whose surface is etched.
  • the CV value product of capacity and formation voltage described later
  • the mass can be 4 O mg or more.
  • the dielectric layer formed on the conductor surface of the present invention includes at least one selected from metal oxides such as T a 2 0 5 , A 1 2 O 3 , T i 0 2 , and N b 2 0 5. Examples thereof include a dielectric layer as a main component. These dielectric layers are formed in an electrolyte containing an organic acid or organic acid salt such as acetic acid, adipic acid, or benzoic acid, or a mineral acid or mineral acid salt such as phosphoric acid, sulfuric acid, boric acid, or silicic acid. It is formed by applying a voltage between the anode side of the conductor and the cathode plate separately arranged in the electrolyte (referred to as “chemical conversion”).
  • an organic acid or organic acid salt such as acetic acid, adipic acid, or benzoic acid
  • a mineral acid or mineral acid salt such as phosphoric acid, sulfuric acid, boric acid, or silicic acid. It is formed by applying a voltage between the anode
  • the formation temperature, formation time, current density during formation, etc. are determined in consideration of the type, mass and size of the conductor, the capacity and operating voltage of the target solid electrolytic capacitor element, and the like.
  • the formation temperature is usually from room temperature to 10 ° C or less, and the formation time is usually from several hours to several hours.
  • the electrolytic solution adhering to the conductor is washed with water or an appropriate organic solvent such as alcohol and then dried.
  • the conductor before providing a semiconductor layer on a conductor formed with a dielectric layer by an energization method, the conductor is impregnated with a dopant so that a dopant is contained in the pores inside the conductor. Is essential. Conductor with finer pores than before The reason is not clear by impregnating with a dopant after forming a dielectric layer on the semiconductor layer, but it is possible to provide a semiconductor layer uniformly deep inside the pores and supply sufficient dopant to the semiconductor layer. be able to.
  • the solid electrolytic capacitor fabricated in this way has a lower ESR and a larger capacity than conventional capacitors with the same volume of conductor.
  • a conventionally known dopant is used as a dopant to be impregnated in a conductor.
  • pyrrole or 3,4-ethylenedioxythiophene is used as a representative monomer, and conductivity is 1 when doped simultaneously with polymerization by electrolytic polymerization.
  • 0 - 1 to 0 3 gives the S ⁇ cm- 1 conductive polymer de one dopant is preferable.
  • a compound having a sulfonic acid group as a dopant and a boron compound in which a rubonic acid is coordinated to a boron atom can be mentioned.
  • Such compounds include benzene sulphonic acid, tonole senophonic acid, xylene sulphonic acid, ethenole benzene sulphonic acid, naphthalene / lefonic acid, anthracene sulphonic acid, benzoquinone sulphonic acid, naphthoquinone sulphonic acid and anthraquinone sulphonic acid
  • Various oligomers or polymers such as sulfonic acid having an aryl group such as sulfonic acid having an alkyl group such as butyl sulfonic acid, hexeno sulfonic acid, and hexyl sulfonic acid, and polybulu sulfonic acid (degree of polymerization: 2 to
  • sulfonic acids and salts of these sulfonic acids (ammonium salts, alkali metal salts, alkaline earth metal salts, transition metal salts such as iron,
  • These compounds may have various substituents, and a plurality of sulfonic acid groups may exist. Examples thereof include 2,6-naphthalenedisulfonic acid, 1,2-ethanedisulfonic acid, and the like. Examples of boron compounds include ammonium borodisalicylate and its hydrate, boro-1,2-carboxybenzene ammonium, and the like. In addition, a dopant may be used in combination with a plurality of dopants.
  • One example of a method for impregnating a conductor with a dopant is to dissolve or partially suspend the dopant in at least one solvent selected from water or an organic solvent.
  • a method of immersing the conductor in the solution and drying the solvent after pulling up can be mentioned. Part of the solvent used may remain in the conductor.
  • the dopant is liquid at room temperature, the conductor may be directly dipped in the dopant without using a solvent and pulled up. After pulling up, drying at a temperature higher than normal temperature or rinsing the conductor surface layer with an appropriate solvent to remove the dopant on the conductor surface and then forming the semiconductor layer in the next step Good. It is preferable to impregnate the conductor with the dopant and remove the solvent in multiple steps, since the dopant is uniformly introduced deep into the conductor.
  • Re-formation may be performed to repair minute defects in the dielectric layer caused by impregnation with the dopant.
  • the re-chemical conversion method can be carried out in the same manner as chemical conversion using the reagent used for the chemical conversion described above. It is also possible to use the dopant used for the dopant impregnation of the conductor in the re-forming reagent. If a dopant is used in the re-formation reagent, the exudation of the dopant from the conductor due to the formation may be mitigated.
  • examples of the other electrode formed on the dielectric layer of the conductor impregnated with the dopant include at least one organic semiconductor selected from conductive polymers described later.
  • these conductive polymers may be included in the first layer, and at least one compound selected from organic semiconductors and inorganic semiconductors may be included as the second layer, or both may be included as a mixture. Good.
  • the organic semiconductor include an organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor composed mainly of tetrathiotetracene, an organic semiconductor composed mainly of tetracyanoquinodimethane, the following general formula (1) or ( Examples thereof include organic semiconductors mainly composed of a conductive polymer obtained by doping a polymer containing a repeating unit represented by 2) with a dopant.
  • R to R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms
  • X represents oxygen, io or nitrogen
  • R 5 is present only when X is a nitrogen atom and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 1 and R 2 and R 3 and R 4 are bonded to each other. It may be annular.
  • the polymer containing the repeating unit represented by the general formula (1) is preferably a polymer containing a structural unit represented by the following general formula (3) as a repeating unit.
  • each of 16 and 17 is independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or an alkyl group thereof. It represents a substituent that is bonded at a position to form a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen atoms.
  • the cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted.
  • a conductive polymer containing such a chemical structure is charged and doped with a dopant.
  • the dopant is not particularly limited, and the conductor is formed before the semiconductor layer is formed.
  • the same materials as mentioned as the dopant to be impregnated can be used.
  • the dopant used in the present invention is described as an uncharged compound, but when it actually acts as a dopant, it is partially charged and ionized (mainly anion).
  • benzenesulfonic acid also includes benzenesulfonic acid anion.
  • the polymer containing repeating units represented by the formulas (1) to (3) include polyaniline, polyoxyfurene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylvillol, And substituted derivatives and copolymers thereof. Of these, polypyrrole, polythiophene, and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene)) are preferable.
  • the semiconductor layer described above is formed in a layered form by chemical polymerization (solution reaction, gas phase reaction, solid-liquid reaction and a combination thereof), electrolytic polymerization, or a combination of these methods. If at least the first layer of the semiconductor layer (the first layer) is prepared using the electrolytic polymerization method, the conductive polymer chain is not branched, or the semiconductor layer thickness on the outer surface of the conductor is uniform. Therefore, it is preferable because the initial ESR value of the capacitor is lower than that of other methods.
  • the inorganic semiconductor include at least one compound selected from molybdenum dioxide, tungsten dioxide, diacid oxide, manganese diacid manganese, and the like.
  • the conductive polymer of the first layer of the semiconductor layer (the entire semiconductor layer if there are no remaining layers) is formed by an energization technique called electrolytic polymerization.
  • An electropolymerization method is known in which an external electrode placed near the outer periphery of a conductor is used as an anode.
  • electricity is applied using the anode portion or anode lead of the conductor as the anode and the cathode plate disposed in the semiconductor layer forming solution in which the conductor is immersed as the cathode.
  • polymerization starts from the inside of the conductor, even a conductor having fine pores is preferably uniformly polymerized, and semiconductor deposition is improved.
  • re-formation may be performed to repair a minute defect in the dielectric layer caused by the formation of the semiconductor layer.
  • the energization and re-formation for forming the semiconductor layer may be repeated a plurality of times, or the energization conditions at the time of repetition may be changed. Normally, when stopping the energization, the conductor is pulled up from the semiconductor layer forming solution to perform cleaning / drying, but the energization / energization stop / cleaning / drying process is repeated several times before entering the re-forming process. Also good. The reason for this is not clear, but the mass of the semiconductor layer may increase if the total energization time is set to the same value, followed by energization, de-energization, cleaning, and drying.
  • Re-chemical conversion can be performed in the same manner as the above-described dielectric layer forming method.
  • the re-forming voltage shall be below the forming voltage.
  • a semiconductor layer may be formed by a method.
  • re-formation may be performed any number of times at any time during the formation of the semiconductor layer, but it is desirable to perform re-formation after the final semiconductor layer is formed.
  • an electrode layer is provided on the semiconductor layer formed by the above-described method or the like.
  • the electrode layer can be formed, for example, by solidifying a conductive paste, plating, metal vapor deposition, adhesion of a heat-resistant conductive resin film, or the like.
  • a conductive paste a silver paste, a copper paste, an ano-reminium paste, a carbon paste, a nickel paste, etc. are preferable, but these may be used alone or in combination of two or more. If two or more types are used, they may be mixed or stacked as separate layers. After applying conductive paste, leave in air or heat to solidify.
  • the main component of the conductive paste is conductive powder such as resin and metal, but a solvent for dissolving the resin and a curing agent for the resin are also used if desired.
  • the solvent will scatter during the heat solidification.
  • the resin various known resins such as alkyd resin, acrylic resin, epoxy resin, phenol resin, imide resin, fluororesin, ester resin, imidoamide resin, amide resin, and styrene resin are used.
  • the conductive powder powders of silver, copper, aluminum, gold, rikibon, nickel, alloys containing these metals as main components, and mixed powders thereof are used.
  • the conductive powder is usually contained in 40 to 97% by mass.
  • the conductive paste may be used by mixing the aforementioned conductive polymer or metal oxide powder forming the semiconductor layer.
  • plating examples include nickel plating, copper plating, silver plating, gold plating, aluminum plating, and the like.
  • Examples of the deposited metal include aluminum, nickel, copper, gold, and silver.
  • an electrode layer is formed by sequentially laminating a carbon paste and a silver paste on the formed semiconductor layer.
  • a solid electrolytic capacitor element is fabricated by stacking the conductor up to the electrode layer.
  • the solid electrolytic capacitor element of the present invention configured as described above is, for example, a resin module.
  • Solid electrolytic capacitor products for various applications can be packaged with metal foil, resin case, metallic outer case, resin dating, and laminating film.
  • a chip-shaped solid electrolytic capacitor with a resin mold is particularly preferable because it can be easily reduced in size and cost.
  • the capacitor according to the present invention will be described in detail.
  • the capacitor according to the present invention has a lead frame (a tip portion disposed so as to be opposed to a gap) with a part of the electrode layer of the capacitor element prepared separately. And a part of the conductor is placed on the other tip of the lead frame. In this case, if the conductor has a structure with an anode lead, the anode You can cut the tip of the card.
  • the cathode and anode of the capacitor element are electrically and mechanically joined to the respective leading ends of the lead frame by solidifying or welding the conductive paste, and a part of the leading end of the lead frame is left. Seal the resin and cut and bend the lead frame at a predetermined part outside the resin seal to fabricate the capacitor chip. (Note that the lead frame is on the bottom surface of the resin seal and only the bottom surface or bottom and side surfaces of the lead frame. If it is sealed with leaving, it may be cut only).
  • the lead frame is finally cut and becomes the external terminals of the capacitor.
  • the shape of the lead frame is foil or flat plate, and the material is mainly iron, copper, aluminum or these metals.
  • the alloy used as a component is used.
  • At least one plating layer of solder, tin, titanium, gold, silver, nickel, palladium, copper, or the like may be applied to a part or all of the lead frame.
  • the lead frame has a pair of opposed tip portions, and the gap between the tip portions insulates the anode portion and the electrode layer portion of each capacitor element.
  • resins used for sealing capacitors such as epoxy resins, phenol resins, alkyd resins, ester resins, and aryl ester resins can be employed.
  • a low-stress resin for example, a resin that usually contains 70% by volume or more of filler and has a thermal expansion coefficient ⁇ of 3 X 10 5 ° or less
  • a transfer machine is preferably used for sealing the resin.
  • the solid electrolytic capacitor thus fabricated may be subjected to an aging treatment to repair the deterioration of the thermal and / or physical dielectric layer during electrode layer formation and exterior.
  • the aging method is performed by applying a predetermined voltage (usually within twice the rated voltage) to the capacitor.
  • Aging time and temperature are determined in advance by experiment because optimum values differ depending on the type, capacity, and rated voltage of the capacitor. Normally, the time is from several minutes to several 3, and the temperature is determined in consideration of the thermal deterioration of the voltage application jig. Performed at 300 ° C or lower.
  • the aging atmosphere may be performed under any conditions of reduced pressure, normal pressure, and increased pressure. Further, the aging atmosphere may be air, a gas such as argon, nitrogen, or helium, but is preferably water vapor. Aging may be performed in an atmosphere containing water vapor, and then in a gas such as air, argon, nitrogen, or helium, and stabilization of the dielectric layer may proceed. After supplying water vapor, return to normal pressure and room temperature, or after supplying water vapor, leave it at a high temperature of 15 to 25 ° C. for several minutes to several hours to remove excess water and perform the above aging Is also possible.
  • a water vapor supply method is a method of supplying water vapor by heat from a water reservoir placed in an aging furnace.
  • the voltage application method can be designed to allow direct current, alternating current with an arbitrary waveform, alternating current superimposed on direct current, and pulsed current. It is also possible to stop the voltage application in the middle of aging and apply the voltage again. Aging may be performed while increasing the voltage in order from the low voltage to the high voltage.
  • the solid electrolytic capacitor manufactured by the present invention can be preferably used for a circuit using a high-capacitance capacitor such as a central processing circuit and a power supply circuit, and these circuits include a personal computer, a server, a camera, a game machine, It can be used for various digital devices such as DVDs, AV devices and mobile phones, and electronic devices such as various power supplies.
  • the solid electrolytic capacitor manufactured by the present invention has a large capacity and a good initial ESR value. By using this solid electrolytic capacitor, a highly reliable electronic circuit and electronic device that generates little heat even when a large current flows are obtained. Can do. Example Hereinafter, specific examples of the present invention will be described in more detail. However, the present invention is not limited to the following examples.
  • Niobium primary powder (average particle size 0.30 ⁇ ) pulverized using the hydrogen embrittlement of niobium ingot is granulated, and niobium powder with an average particle size of 1 30 ⁇ Oxygen is present at 105000 ppm).
  • niobium powder with an average particle size of 1 30 ⁇ Oxygen is present at 105000 ppm.
  • it is left in a nitrogen atmosphere at 45 ° C. and then in argon at 70 ° C., so that it is partially nitrided niobium powder (C V297000 // F- V / g).
  • This niobium powder was formed with a 0.48mm diameter niobium wire and sintered at 1270 ° C to produce multiple sintered bodies (conductors) of size 4.1 X 3.5 X 1.0mm (each mass 0.06 g The tube leads are 3.7 mm inside the sintered body and 8 mm outside.
  • a dielectric mainly composed of niobium pentoxide is formed on the sintered body surface and part of the lead wire.
  • a body layer was formed.
  • the sintered body was subsequently immersed in an alcohol solution in which the compound described in Table 1 as a dopant was dissolved, and then dried to remove the alcohol. Such dopant impregnation and alcohol removal were repeated 10 times. Next, the surface of the conductor was washed with alcohol and dried.
  • the sintered body was prepared in a tank containing a mixed solution of 30% by mass ethylene glycol and water in which a small amount of pyrrole monomer and 4% anthraquinone-2-sulfonic acid were separately prepared. Electrode polymerization at 100 A for 60 minutes with the lead wire of the sintered body as the anode and the external electrode as the cathode for 60 minutes, withdrawn from the tank, and washed with water After alcohol washing and drying, re-formation was performed in 1% by weight phosphoric acid aqueous solution at 70 ° C and 13 V for 15 minutes. This electrolytic polymerization and re-formation were repeated 6 times to form a semiconductor layer made of polypyrrole on the dielectric layer.
  • a carbon paste is laminated on the semiconductor layer and dried to form a carbon layer.
  • a silver paste mainly composed of 90% by mass of silver powder and 10% by mass of acrylic resin was laminated and then dried to form an electrode layer, thereby producing a plurality of solid electrolytic capacitor elements.
  • the lead wire on the sintered body side and the electrode layer side on a pair of both ends of a lead frame (10 ⁇ semi-bright nickel plating on both sides of the copper alloy), which is a separately prepared external terminal The former was spot welded, and the latter was connected electrically and mechanically with the same silver paste used for the electrode layer.
  • a chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 1 except that the conductor in which the dielectric layer was formed in Example 1 was not impregnated with the dopant.
  • Example 4
  • Example 2 The electrolytic polymerization in Example 1, carried out at a bath 4% naphthalene one 2-sulfonic acid containing 3 0 mass 0/0 mixed solution of ethylene da recall and water dissolved in place of 4% anthraquinone one 2- sulfonic acid A chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 1 except that. Comparative Example 2:
  • a chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 4 except that the conductor in which the dielectric layer was formed in Example 4 was not impregnated with the dopant.
  • a chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 5 except that the conductor in which the dielectric layer was formed in Example 5 was not impregnated with the dopant.
  • Example 9 the conductor in which the dielectric layer was formed in Example 5 was not impregnated with the dopant.
  • the capacitor was set in the same manner as in Example 5 except that the size of the sintered body was 4.4X3.0X3.0mm, the mass was 245 mg, and the size of the chip-shaped solid electrical square capacitor was 7.3X4.3X3.8mm. Produced. Comparative Example 4:
  • a chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 9 except that the conductor on which the dielectric layer was formed in Example 9 was not impregnated with the dopant.
  • the performances of the chip-shaped solid electrolytic capacitors produced in Examples 1 to 9 and Comparative Examples 1 to 4 were measured by the following method, and are summarized in Table 2.
  • the data in Table 2 is the average value of 30 capacitors.
  • Capacity Measured at 12 OHz at room temperature using an LCR measuring instrument manufactured by Huylet Packard.
  • E S R The equivalent series resistance of the capacitor was measured at 100 kHz.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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Abstract

L’invention décrit un procédé de fabrication d’un élément de condensateur à électrolyte solide, dans lequel le condensateur ayant une couche diélectrique à la surface est pourvu d’une couche semi-conductrice contenant un polymère conducteur. Particulièrement, l’élément de condensateur à électrolyte solide est fabriqué en imprégnant un conducteur ayant une couche diélectrique à la surface avec un dopant puis en y appliquant un courant pour former une couche semi-conductrice. En utilisant l’élément de condensateur à électrolyte solide ainsi fabriqué, on peut obtenir un condensateur à électrolyte solide à haute capacité de bonne résistance série (ESR).
PCT/JP2005/024155 2004-12-24 2005-12-22 Element de condensateur a electrolyte liquide, condensateur a electrolyte liquide et leur procede de fabrication WO2006068302A1 (fr)

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JP2004373651 2004-12-24
JP2004-373651 2004-12-24

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WO2006068302A1 true WO2006068302A1 (fr) 2006-06-29

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258818A (ja) * 1988-08-25 1990-02-28 Nippon Chemicon Corp 固体電解コンデンサの製造方法
JPH02249221A (ja) * 1989-03-23 1990-10-05 Asahi Glass Co Ltd 固体電解コンデンサ
WO2003032344A1 (fr) * 2001-10-02 2003-04-17 Showa Denko K.K. Poudre de niobium, compact fritte associe, produit modifie chimiquement associe et condensateur utilisant lesdits compact et produit

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW502266B (en) * 1999-04-06 2002-09-11 Showa Denko Kk Solid electrolytic capacitor and method for producing the same
JP4566593B2 (ja) * 2003-04-14 2010-10-20 昭和電工株式会社 焼結体電極及びその焼結体電極を用いた固体電解コンデンサ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258818A (ja) * 1988-08-25 1990-02-28 Nippon Chemicon Corp 固体電解コンデンサの製造方法
JPH02249221A (ja) * 1989-03-23 1990-10-05 Asahi Glass Co Ltd 固体電解コンデンサ
WO2003032344A1 (fr) * 2001-10-02 2003-04-17 Showa Denko K.K. Poudre de niobium, compact fritte associe, produit modifie chimiquement associe et condensateur utilisant lesdits compact et produit

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TWI469163B (zh) 2015-01-11

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