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WO1997036303A1 - Composition de pate pour la preparation d'un electrolyte solide et procede de fabrication d'un condensateur electrolytique solide - Google Patents

Composition de pate pour la preparation d'un electrolyte solide et procede de fabrication d'un condensateur electrolytique solide Download PDF

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Publication number
WO1997036303A1
WO1997036303A1 PCT/JP1997/000974 JP9700974W WO9736303A1 WO 1997036303 A1 WO1997036303 A1 WO 1997036303A1 JP 9700974 W JP9700974 W JP 9700974W WO 9736303 A1 WO9736303 A1 WO 9736303A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
forming
paste composition
manganese dioxide
electrolytic capacitor
Prior art date
Application number
PCT/JP1997/000974
Other languages
English (en)
Japanese (ja)
Inventor
Takafumi Dohdoh
Takehiro Shimizu
Original Assignee
Hitachi Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co., Ltd. filed Critical Hitachi Chemical Co., Ltd.
Publication of WO1997036303A1 publication Critical patent/WO1997036303A1/fr

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Classifications

    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material

Definitions

  • the present invention relates to a paste composition for forming a solid electrolyte and a method for producing a solid electrolytic capacitor using the same.
  • the present invention relates to a paste composition for forming a solid electrolyte used for forming an electrode layer on an electronic component such as a capacitor, and a method for producing a solid electrolytic capacitor using the same.
  • a manganese dioxide layer or the like having an arbitrary thickness.
  • a cathode layer is formed by successively applying carbon, silver paste, and the like.
  • a manufacturing method is used in which an external lead is soldered after the application and the resin is packaged by a resin dipping method, a resin molding method, or the like.
  • the thickness of the coating layer that can be formed at one time during the thermal decomposition step of the chemical conversion treatment is extremely small. It was necessary to repeat the pyrolysis process several times to several times to form the slag, and there was a problem that the time required and the energy cost were extremely large. Also, nitric acid manga In the pyrolysis process, NO was generated due to the thermal decomposition of gas, and there were also environmental problems such as the treatment of these decomposition gases.
  • this method makes it difficult for the thickness of the manganese dioxide layer and the like to be uniform, and if this thickness is small, the carbon layer directly contacts the oxide film and leaks. There was a problem that the current easily increased.
  • the manganese dioxide layer and the like are thicker at the corners than at the other parts. There was a problem that the water resistance and moisture resistance were reduced.
  • the resin sheathing is performed by the resin dipping method, the dimensions are likely to vary, and when the resin sheath shrinks, the corners are stressed and the characteristics are likely to deteriorate.
  • Japanese Patent Application Laid-Open No. 51-76559 describes that manganese dioxide powder is mixed into volatile solvents such as water, alcohol, thinner, carbon tetrachloride, and ammonium carbonate. A method is disclosed. However, in this method, the manganese dioxide powder in the solution is difficult to disperse, and the particles agglomerate during storage. Sedimentation occurs, making it difficult to obtain a uniform coating film.
  • Japanese Patent Application Laid-Open No. 7-233298 discloses a method of replacing a part of the metal powder used for the conductive base with manganese dioxide powder. In this method, however, a solid electrolyte is used. All the properties could not be fully realized.
  • the present invention has been made to solve the above-mentioned problems, and a paste composition for forming a solid electrolyte capable of forming a uniform coating film in which manganese dioxide powder is unlikely to settle, and an electrolytic solution.
  • a method for manufacturing a solid electrolytic capacitor using the base composition which can shorten the manufacturing time of a capacitor, improve leakage current characteristics, heat resistance, moisture resistance, etc., and improve the accuracy of external dimensions.
  • the purpose is to do. Disclosure of the invention
  • the present invention has the following gist to achieve the above object.
  • a paste composition for forming a solid electrolyte comprising (A) manganese dioxide powder, (B) a dispersing resin and (C) a dispersing medium as essential components. Since this composition has excellent conductivity and can obtain a predetermined film thickness by one application, it is suitable for forming a solid electrolyte layer of a tantalum capacitor element.
  • this composition can improve the conductivity of the manganese dioxide powder itself and reduce the resistance of the coating film.
  • the dispersing resin is cellulose and its derivatives, polyglycols, polyacrylic acid, polyacrylic acid soda, polyacrylinoleamide, polyvinyl vinylidone, polydisperse resin.
  • Vinyl ether, water-soluble alk Is a water-soluble polymer resin selected from the group consisting of polymethacrylate, polymaleic acid copolymer, polyethylenimine and polyvinyl alcohol [1] to [
  • the paste composition for forming a solid electrolyte according to any one of the above.
  • a water-soluble polymer resin as the dispersing resin, the composition can be easily dispersed in a dispersing medium and can provide a stable paste composition for forming a solid electrolyte. .
  • the dispersion medium is at least one organic solvent or pure water selected from the group consisting of alcohols, ethylene glycols and propylene glycols, or a mixture thereof [1] to
  • manganese dioxide powder is easily prepared by using an organic solvent selected from alcohol, ethylene glycol, and propylene glycol, or pure water, or a mixture thereof as a dispersion medium. And a stable solid electrolyte layer can be formed.
  • This method can provide a method for manufacturing a solid electrolytic capacitor capable of shortening the manufacturing time, improving leakage current characteristics, heat resistance, moisture resistance, and improving the accuracy of external dimensions.
  • FIG. 1 shows a characteristic graph of equivalent series resistance ESR of Examples 7 and 8 of the present invention and Comparative Example 3.
  • FIG. 2 shows characteristic graphs of leakage currents of Examples 7 and 8 and Comparative Example 3 of the present invention.
  • the paste composition for forming a solid electrolyte of the present invention contains (A) manganese dioxide powder, (B) a dispersion resin and (C) a dispersion medium as essential components.
  • Examples of the (A) manganese dioxide powder used in the present invention include powders having an ⁇ -type, a type, a 7-type or a type crystal structure, and include a type crystal structure in consideration of conductivity.
  • Manganese dioxide powder is preferred.
  • Manganese dioxide containing Form 3 can be easily obtained by heating manganese dioxide at 250 ° C to 400 ° C for 1 to 5 hours.
  • the average particle size of the manganese dioxide powder is 0.01 !, considering the conductivity and the applicability of the paste. Those with a size of ⁇ 50 are preferred, and those with a value of 0.01-10 ⁇ m are more preferred.
  • the shape of the manganese dioxide powder is not limited to such a force as exemplified by a sphere, an irregular shape, and a crushed shape.
  • the blending amount of the manganese dioxide powder in the present invention is preferably 1 to 90% by weight of the total amount of (A) manganese dioxide powder (B) dispersed resin and (C) dispersion medium, and is preferably 5 to 80%. %, More preferably 20% to 70% by weight. If the content is less than 1% by weight, it is difficult to form a coating film and the solid electrolyte functions as a solid electrolyte. When the content exceeds 9-0 unit amount%, the coatability as a paste and the adhesiveness to a substrate tend to decrease.
  • the (B) dispersed resin used in the present invention is (A) one that improves the dispersibility of the manganese dioxide powder, water-soluble, and (A) one that easily binds to the manganese dioxide powder.
  • derivatives such as cenorellose, methinoresenolylose, ethylcellulose, carboxymethylcellulose, and hydroxyshethylcellulose, polyethylene glycol, and polypropylene glycol
  • Polyacrylic acid, polyacrylic acid, polyacrylic acid soda, polyacrylamide, polyvinyl borolidone, water-soluble alkyd, polyvinyl ether, polymalein Acid copolymers, polyethyleneimine and polyvinyl alcohol are exemplified as being preferred.
  • the compounding amount of (B) the dispersing resin is 0.5 to 40% by weight of the total amount of (A) manganese dioxide powder, (B) the dispersing resin and (C) the dispersing medium.
  • the content is preferably 1 to 20% by weight, more preferably 2 to 10% by weight. If the amount is less than 0.5% by weight, the dispersion of manganese dioxide tends to be insufficient. If the amount exceeds 40% by weight, the conductivity tends to decrease and the performance as a solid electrolyte tends to deteriorate. is there.
  • the (C) dispersion medium used in the present invention is not particularly limited as long as it can dissolve the (B) dispersion resin and maintain the dispersion stability of (A) manganese dioxide powder, but are not limited to alcohol-based dispersion media.
  • the preferred solvent include an ethylene glycol-based or propylene glycol-based organic solvent, or pure water or pure water in which a manganese salt such as manganese nitrate is dissolved. Is done. -.
  • organic solvents or pure water may be used alone or in a combination of two or more at any ratio.
  • the blending amount of (C) the dispersion medium is preferably 10 to 95% by weight of the total amount of (A) manganese dioxide powder, (B) the dispersion resin, and (C) the dispersion medium.
  • the content is more preferably from 20 to 90% by weight, and particularly preferably from 25 to 80% by weight. If the compounding power is less than 10% by weight, the dispersion of the manganese dioxide powder becomes insufficient, and if it exceeds 95% by weight, the film thickness of the coating film becomes too thin to obtain a sufficient film thickness at one time. Tend.
  • (D) a coupling agent as necessary in order to stably disperse (A) manganese dioxide.
  • the method of using the coupling agent is as follows: (A) manganese dioxide, (B) dispersing resin, and (C) dispersing medium by directly adding to (A) There is a method in which manganese dioxide powder is used after treatment with (D) a capping agent.
  • the method of treating manganese dioxide powder includes, for example, (A) a method of adding (D) a coupling agent directly to manganese dioxide powder and mixing with stirring (dry treatment method) and a method of hexane.
  • a coupling agent is preliminarily dissolved in a solvent such as toluene or the like, and (A) manganese dioxide powder is added thereto, mixed and stirred, and then the solvent is removed and dried (wet processing method).
  • the paste composition for forming a solid electrolyte of the present invention may be, for example, an antioxidant, a chelating agent, or an additive having various functions, as long as it does not adversely affect the properties of the cured product when the paste and the coating film are formed.
  • a modifier and the like can be added.
  • carbon black, graphite carbon, or the like can be used in combination to impart conductivity. The amount of these is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the manganese dioxide powder.
  • the base composition for forming a solid electrolyte of the present invention may be prepared by mixing a predetermined amount of (A) manganese dioxide powder, (B) a dispersion resin and (C) a dispersion medium with an ordinary stirrer, triturator, three-roll or roll mill. It can be easily obtained by uniformly kneading or dispersing using a solvent or the like, and a uniform and thick coating film can be obtained by one application without changing the characteristics as a solid electrolyte. It can be suitably used as a solid electrolyte layer such as a tantalum capacitor.
  • the present invention relates to a method for producing a solid electrolytic capacitor using the paste composition for forming a solid electrolyte.
  • a solid electrolytic capacitor can be obtained by forming an anodized film on a sintered body obtained from a valve metal powder or by immersing the sintered body with the anodized film in a semiconductor mother liquor and thermally decomposing it. Immersed in the paste composition for solid electrolyte formation described above and dried Thus, a solid electrolytic capacitor is manufactured by forming a semiconductor layer.
  • a valve metal such as tantalum is embedded in one end of a tantalum lead wire or the like, the other end is drawn out, compression-molded with a press, and then pressed in a vacuum. Heat at a temperature of about 100 ° C for several 10 minutes to form a sintered body. Next, the sintered body is welded to a metal bar such as stainless steel at a place such as a tan wire, and the sintered body is formed by applying a voltage in a chemical solution such as nitric acid and phosphoric acid. , An anodic oxide film of Ta 2 O, is formed.
  • the sintered body having the anodic oxide film formed thereon is immersed in a semiconductor mother liquor such as a manganese nitrate solution to be impregnated with the solution, and then baked at a temperature of 200 ° C. to 350 ° C. to undergo thermal decomposition. Then, a semiconductor layer mainly including a manganese dioxide layer is formed inside the sintered body, and then re-formed to repair the anodized film damaged by sintering.
  • a semiconductor mother liquor such as a manganese nitrate solution to be impregnated with the solution
  • a semiconductor layer mainly including a manganese dioxide layer is formed inside the sintered body, and then re-formed to repair the anodized film damaged by sintering.
  • Manganese dioxide powder (RB-A manufactured by Mitsui Kinzoku Co., Ltd.) was heated at 350 ° C for 3 hours. (Average particle size: 2 m) 10 Q Add 60 parts by weight of n-hexane and 1 part by weight of AL-M (Ajinomoto Co., Alumino-based coupling agent) Then, the mixture was stirred and mixed with a roll mill. Thereafter, n-hexane was removed to obtain a manganese dioxide powder having a surface-treated type crystal structure.
  • AL-M Al-M
  • the conductivity was measured by forming a coating film of about 50 m on a ceramic plate by screen printing, and after curing, using a digital multimeter by a four-terminal method.
  • the dispersibility was measured using a grain gauge according to the method of JIS-K540.
  • the thickness of the coating was measured by dipping a ceramic plate of 1 ⁇ 2 cm in a paste for about 3 seconds, pulling it up, drying it, and measuring the coating thickness using a micrometer.
  • Example 1 100 parts by weight of the surface-treated manganese dioxide powder having a / 5-type crystal structure used in Example 1 was added to 5 parts by weight of sodium polyacrylate (AC_103) and the product AL— After preliminarily mixing 2 parts by weight of M and 40 parts by weight of pure water in a mortar, the mixture was kneaded with three rolls to obtain a paste composition for forming a solid electrolyte.
  • Table 1 shows the conductivity, dispersibility, and coating film thickness of this base composition.
  • Example 4 The same procedure as in Example 1 was carried out except that a 50% by weight aqueous solution of manganese nitrate was used as the dispersion medium. Table 1 shows the dispersibility and coating film thickness. [Example 4]
  • Example 1 The same procedure as in Example 1 was carried out except that the dispersing resin and polyvinylpyrrolidone (manufactured by ISBI JAPAN Co., Ltd.) were used, and the conductivity, dispersibility, Table 1 shows the coating thickness.
  • a manganese dioxide layer is formed on a ceramic substrate by a conventional method of thermally decomposing a 50% by weight aqueous solution of manganese nitrate without using a paste composition in which manganese dioxide powder is dispersed to form a conductive and coated film.
  • Table 1 shows the results of the examination.
  • the conductive paste composition of the present invention had good dispersibility and excellent conductivity, and was able to obtain a predetermined film thickness by one application. .
  • Example 1 To form a manganese dioxide layer, the sintered body was immersed in a manganese nitrate solution, and the process of thermal decomposition and re-chemical formation by chemical formation was repeated eight times, and the paste composition for forming a solid electrolyte formed in Example 1 was obtained.
  • a solid electrolytic capacitor according to a conventional method was manufactured under the same conditions as in Example 6, except that no material was used.
  • Example 6 shows the same characteristics as Comparative Example 2. That is, it was clarified that Example 6 exhibited good characteristics even when a series of steps such as immersion in a manganese nitrate solution and thermal decomposition were performed 1 to 2 times in the comparative example which is a conventional method.
  • Example 6 After repeating the series of processes of immersing the sintered body in a manganese nitrate solution, sintering, and re-forming as shown in Example 6 three times, the solid electrolyte-forming paste composition prepared in Example 1 was used as a stock solution.
  • a solid electrolytic capacitor was produced under the same conditions as in Example 6, except that the immersion and drying treatments were repeated twice to form a manganese dioxide layer.
  • An electrolytic capacitor was manufactured.
  • a solid electrolytic capacitor was produced by the conventional method under the same conditions as in Comparative Example 2, except that the sintered body was immersed in a manganese nitrate solution, and the steps of thermal decomposition and re-chemical formation by chemical conversion were repeated six times.
  • both ESR and LC have the same or better characteristics as those of Comparative Example 3. It is also clear that a range of 180 to 200 for both properties is a particularly preferred drying temperature.
  • the paste composition for forming a solid electrolyte of the present invention is suitable for uniformly forming a solid electrolyte of an electronic component such as a solid electrolytic capacitor such as an indium capacitor.
  • the method for producing a solid electrolytic capacitor using the paste composition for forming is effective for producing a solid electrolytic capacitor such as a tantalum capacitor in a short time and with high accuracy.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne une composition de pâte destinée à la préparation d'un électrolyte solide et renfermant (A) une poudre d'oxyde de manganèse, (B) une résine de dispersion et (C) un milieu de dispersion constituant les composants essentiels, ainsi qu'un procédé de préparation d'un condensateur électrolytique solide à l'aide de la composition. Cette composition de pâte présente une excellente conductivité. Il est possible de former un film d'une épaisseur donnée grâce à une seule application de cette composition de pâte. Lorsqu'on met en ÷uvre ce procédé de fabrication de condensateur électrolytique solide à l'aide de la composition de pâte, le temps de fabrication du condensateur électrolytique solide peut être raccourci. Par ce procédé, il est possible d'améliorer les caractéristiques du courant de fuite, la résistance à la chaleur et la résistance à l'humidité du condensateur et d'obtenir des dimensions externes plus précises.
PCT/JP1997/000974 1996-03-26 1997-03-24 Composition de pate pour la preparation d'un electrolyte solide et procede de fabrication d'un condensateur electrolytique solide WO1997036303A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6955996 1996-03-26
JP8/69559 1996-03-26

Publications (1)

Publication Number Publication Date
WO1997036303A1 true WO1997036303A1 (fr) 1997-10-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2489786A (en) * 2011-04-07 2012-10-10 Avx Corp Hermetically sealed solid electrolytic capacitor assembly containing an inert gas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59197123A (ja) * 1983-04-23 1984-11-08 エルナ−株式会社 電解コンデンサおよびその製造方法
JPS6047734B2 (ja) * 1981-10-12 1985-10-23 日立コンデンサ株式会社 固体電解コンデンサの製法
JPS63104319A (ja) * 1986-10-21 1988-05-09 マルコン電子株式会社 積層形ペ−パ−レス電解コンデンサの製造方法
JPS63119518A (ja) * 1986-11-08 1988-05-24 昭和電工株式会社 固体電解コンデンサ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6047734B2 (ja) * 1981-10-12 1985-10-23 日立コンデンサ株式会社 固体電解コンデンサの製法
JPS59197123A (ja) * 1983-04-23 1984-11-08 エルナ−株式会社 電解コンデンサおよびその製造方法
JPS63104319A (ja) * 1986-10-21 1988-05-09 マルコン電子株式会社 積層形ペ−パ−レス電解コンデンサの製造方法
JPS63119518A (ja) * 1986-11-08 1988-05-24 昭和電工株式会社 固体電解コンデンサ

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2489786A (en) * 2011-04-07 2012-10-10 Avx Corp Hermetically sealed solid electrolytic capacitor assembly containing an inert gas
US8947857B2 (en) 2011-04-07 2015-02-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
GB2489786B (en) * 2011-04-07 2015-04-15 Avx Corp Manganese oxide capacitor for use in extreme environments
US9508492B2 (en) 2011-04-07 2016-11-29 Avx Corporation Manganese oxide capacitor for use in extreme environments
US10014120B2 (en) 2011-04-07 2018-07-03 Avx Corporation Manganese oxide capacitor for use in extreme environments

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