JPH0864476A - Method of manufacturing solid-state electrolytic capacitor - Google Patents
Method of manufacturing solid-state electrolytic capacitorInfo
- Publication number
- JPH0864476A JPH0864476A JP19638794A JP19638794A JPH0864476A JP H0864476 A JPH0864476 A JP H0864476A JP 19638794 A JP19638794 A JP 19638794A JP 19638794 A JP19638794 A JP 19638794A JP H0864476 A JPH0864476 A JP H0864476A
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- electrolytic capacitor
- layer
- conductive polymer
- polypyrrole
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000001923 cyclic compounds Chemical class 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007784 solid electrolyte Substances 0.000 description 7
- ROSDCCJGGBNDNL-UHFFFAOYSA-N [Ta].[Pb] Chemical compound [Ta].[Pb] ROSDCCJGGBNDNL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical group CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- YZVMBKNEDSQMFN-UHFFFAOYSA-N CO.C(CCCCCCCCCCC)S(=O)(=O)O Chemical compound CO.C(CCCCCCCCCCC)S(=O)(=O)O YZVMBKNEDSQMFN-UHFFFAOYSA-N 0.000 description 1
- -1 TCNQ salt Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機導電性高分子材料を
固体電解質として用いた固体電解コンデンサの製造方法
に関し、特に良質な固体電解質層を形成できる固体電解
コンデンサの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid electrolytic capacitor using an organic conductive polymer material as a solid electrolyte, and more particularly to a method for producing a solid electrolytic capacitor capable of forming a good quality solid electrolyte layer.
【０００２】[0002]
【従来の技術】従来、固体電解コンデンサは、タンタル
やアルミニウム等の弁作用を有する金属の表面を酸化し
て誘電体酸化皮膜を形成し、その誘電体酸化皮膜上に二
酸化マンガン、二酸化鉛、テトラシアノキノジメタン錯
塩（以下、ＴＣＮＱ塩と記す）等の固体電解質層、導電
ペースト層を順次形成して、コンデンサ素子を作製し、
このコンデンサ素子に外部電極リードを取付け、エポキ
シ樹脂で外装した構造のものがよく知られている。2. Description of the Related Art Conventionally, solid electrolytic capacitors oxidize the surface of a metal having a valve action such as tantalum or aluminum to form a dielectric oxide film, and manganese dioxide, lead dioxide, or tetra-dioxide is formed on the dielectric oxide film. A solid electrolyte layer such as a cyanoquinodimethane complex salt (hereinafter referred to as TCNQ salt) and a conductive paste layer are sequentially formed to produce a capacitor element,
It is well known that the capacitor element has an external electrode lead attached and is covered with an epoxy resin.
【０００３】しかし、最近、電子機器の小型化、高速
化、デジタル化に伴い、コンデンサとしても、高周波領
域での特性の良好なコンデンサが要求されており、それ
に対して、二酸化マンガン、二酸化鉛等を固体電解質と
して使用するものは、その導電率が十分低くないため、
高周波領域での等価直列抵抗（以下、ＥＳＲと記す）が
高くなり、インピーダンスが大きいという問題があり、
また、ＴＣＮＱ錯塩を固体電解質として使用するもの
は、ＴＣＮＱ錯塩が熱分解しやすく耐熱性が劣っている
という問題があった。However, recently, with the downsizing, speeding up, and digitalization of electronic devices, capacitors having good characteristics in a high frequency region have been required, and manganese dioxide, lead dioxide, etc. have been demanded. What is used as a solid electrolyte, because its conductivity is not low enough,
There is a problem that the equivalent series resistance (hereinafter referred to as ESR) in the high frequency region becomes high and the impedance is large,
Further, the one using the TCNQ complex salt as a solid electrolyte has a problem that the TCNQ complex salt is easily decomposed by heat and the heat resistance is poor.
【０００４】そこで、固体電解質として導電率の高いポ
リピロール等の芳香族系導電性高分子化合物を用いた固
体電解コンデンサが提案されている。（特開平３−１２
７８１３号公報、特開昭６３−１８３０９号公報参照）
この固体電解質としてポリピロールを用いた固体電解コ
ンデンサについて、図面を参照して説明する。Therefore, there has been proposed a solid electrolytic capacitor using an aromatic conductive polymer compound such as polypyrrole having high conductivity as the solid electrolyte. (JP-A-3-12
7813, JP-A-63-18309)
A solid electrolytic capacitor using polypyrrole as the solid electrolyte will be described with reference to the drawings.
【０００５】図６に示すように、中央部にタンタルリー
ド１を植立したタンタル焼結体２をリン酸水溶液中で９
０Ｖで陽極酸化し、洗浄、乾燥して五酸化タンタルの誘
電体酸化皮膜３を形成したペレットを作成する。つい
で、このペレットを２０ｗｔ％のドデシベルスルフォン
酸第二鉄塩のメタノール溶液に浸漬し、乾燥後、１００
％のピロール溶液に浸漬し、化学酸化重合して導電性ポ
リピロール層４を形成する。その後、０．００１ｗｔ％
〜１．０ｗｔ％のリン酸水溶液中で電解処理を実施し
て、乾燥後、ポリピロール層４の表面にグラファイト層
５、銀ペースト層６を塗布形成してコンデンサ素子を得
る。このコンデンサ素子に外部導出リード７、８をそれ
ぞれタンタルリード１および銀ペースト層６に接続し、
樹脂９で外装して固体電解コンデンサが得られる。As shown in FIG. 6, a tantalum sintered body 2 in which a tantalum lead 1 is planted at the center is placed in a phosphoric acid aqueous solution 9
Anodization is performed at 0 V, washing and drying are performed to prepare pellets on which the dielectric oxide film 3 of tantalum pentoxide is formed. Then, the pellets were dipped in a 20 wt% ferric dodecyl sulfonic acid salt solution in methanol, dried, and then cooled to 100%.
% Pyrrole solution and chemically oxidatively polymerize to form the conductive polypyrrole layer 4. After that, 0.001 wt%
Electrolytic treatment is carried out in a phosphoric acid aqueous solution of about 1.0 wt%, and after drying, a graphite layer 5 and a silver paste layer 6 are formed by coating on the surface of the polypyrrole layer 4 to obtain a capacitor element. External lead-outs 7 and 8 are connected to the tantalum lead 1 and the silver paste layer 6, respectively, to this capacitor element,
A solid electrolytic capacitor is obtained by coating with resin 9.
【０００６】ところで、このように化学酸化重合で作成
したポリピロール層４は、粗面の誘電体酸化皮膜の微細
孔や空隙への生成効率が低いため、０．００１ｗｔ％〜
１．０ｗｔ％のリン酸水溶液中で電解酸化処理して修復
する。また、化学酸化重合では、ドデシベルスルフォン
酸基がドーパントとして、ポリピロール層４や誘電体酸
化皮膜３とポリピロール層４との接合界面に有効に配置
していないため、この電解酸化処理により有効に配置す
る機能も有している。しかし、この電解酸化処理により
ポリピロールが分解してグラファイト化することがあ
り、この電解酸化処理の条件を非常に精密に制御して
も、均一なＴａｎδ、ＥＳＲ特性が得られないという問
題があった。By the way, the polypyrrole layer 4 thus formed by the chemical oxidative polymerization has a low generation efficiency into the fine pores and voids of the dielectric oxide film on the rough surface, so that 0.001 wt% to
It is repaired by electrolytic oxidation treatment in a 1.0 wt% phosphoric acid aqueous solution. Further, in the chemical oxidative polymerization, since the dodecibel sulfonic acid group is not effectively arranged as a dopant at the bonding interface between the polypyrrole layer 4 and the dielectric oxide film 3 and the polypyrrole layer 4, it is effectively arranged by this electrolytic oxidation treatment. It also has a function to do. However, polypyrrole may be decomposed and graphitized by this electrolytic oxidation treatment, and even if the conditions of this electrolytic oxidation treatment are controlled very precisely, there was a problem that uniform Tan δ and ESR characteristics could not be obtained. .
【０００７】そこで、特開平３−６４０１４号公報に、
図７にしめすような、五酸化タンタルの誘電体酸化皮膜
３を形成したペレットに、化学酸化重合により薄いポリ
ピロール膜１０を界面活性剤を添加して形成し、さら
に、この薄いポリピロール膜１０を電極として、電解酸
化重合により所定の厚さのポリピロール膜１１を形成す
ることにより、上記問題を解決する技術が開示されてい
る。Then, in Japanese Patent Laid-Open No. 3-64014,
As shown in FIG. 7, a thin polypyrrole film 10 is formed by chemical oxidation polymerization on a pellet on which a dielectric oxide film 3 of tantalum pentoxide is formed, and a thin polypyrrole film 10 is formed on the electrode. As a technique, a technique for solving the above problem is disclosed by forming a polypyrrole film 11 having a predetermined thickness by electrolytic oxidation polymerization.
【０００８】[0008]
【発明が解決しようとする課題】ところが、上述した界
面活性剤を添加して、化学酸化重合によりポリピロール
膜を形成する方法では、残存する界面活性剤の量を少な
くするため、化学酸化重合膜を薄く形成した後、電解酸
化重合によるポリピロール膜を厚く形成するという複雑
でしかも処理時間の長い工程を必要とする問題があっ
た。さらに、残存した界面活性剤による特性の劣化を完
全に防止できないという問題もあった。本発明の目的
は、上記の問題を解決し、界面活性剤の添加をせずに、
化学酸化重合のみで、良質のポリピロール膜を形成でき
る固体電解コンデンサの製造方法を提供することにあ
る。However, in the method of forming a polypyrrole film by chemical oxidation polymerization by adding the above-mentioned surfactant, in order to reduce the amount of the surfactant remaining, the chemical oxidation polymerization film is used. There has been a problem that a complicated and long process step of forming a thick polypyrrole film by electrolytic oxidation polymerization after forming a thin film is required. Further, there is a problem that the deterioration of the characteristics due to the remaining surfactant cannot be completely prevented. An object of the present invention is to solve the above problems and to add a surfactant,
An object of the present invention is to provide a method for producing a solid electrolytic capacitor capable of forming a high quality polypyrrole film only by chemical oxidative polymerization.
【０００９】[0009]
【課題を解決するための手段】弁作用を有する金属から
なる陽極の表面に誘電体酸化皮膜を形成し、前記誘電体
酸化皮膜上に有機導電性高分子層を化学酸化重合により
形成し、次いで有機溶剤とリン酸とを混合した液を用い
て電解処理し、その後グラファイト層および導電ペース
ト層を順次塗布して陰極層を形成する固体電解コンデン
サの製造方法を提供する。また、前記有機導電性高分子
層がポリピロール膜であり、前記有機溶剤がアルコール
系溶剤であり、前記有機溶剤とリン酸の混合液のリン酸
濃度が０．００１ｗｔ％乃至１．０ｗｔ％であることを
特徴とする。Means for Solving the Problems A dielectric oxide film is formed on the surface of an anode made of a metal having a valve action, and an organic conductive polymer layer is formed on the dielectric oxide film by chemical oxidative polymerization. Provided is a method for producing a solid electrolytic capacitor in which a cathode layer is formed by performing electrolytic treatment using a liquid mixture of an organic solvent and phosphoric acid and then sequentially applying a graphite layer and a conductive paste layer. Further, the organic conductive polymer layer is a polypyrrole film, the organic solvent is an alcohol solvent, and the phosphoric acid concentration of the mixed solution of the organic solvent and phosphoric acid is 0.001 wt% to 1.0 wt%. It is characterized by
【００１０】[0010]
【作用】上記製造方法によれば、有機導電性高分子と親
和性の良好な有機溶剤とリン酸との混合液中で電解処理
されるため、化学酸化重合で形成された有機導電性高分
子層に注入されているドデシベルスルフォン酸基等のド
ーパントがポリピロール等の有機導電性高分子膜および
誘電体酸化皮膜と有機導電性高分子膜との接合界面に有
効に配置されるとともに、ポリピロール層が小さいエネ
ルギーで修復されるため、ポリピロールが分解してグラ
ファイト化するのを防止でき、静電容量の減少やＥＳＲ
の増加が生ぜず、均一な特性の固体電解コンデンサを製
造できる。また、界面活性剤等の特性を劣化させる物質
を使用せず、しかも、電解酸化重合による有機導電性高
分子膜の形成工程も不要で、化学酸化重合のみで良質の
有機導電性高分子膜の形成が可能となる。According to the above-mentioned manufacturing method, the organic electroconductive polymer formed by chemical oxidative polymerization is electrolyzed in a mixed solution of an organic solvent having a good affinity with the organic electroconductive polymer and phosphoric acid. The dopant such as dodecyl sulfonic acid group injected into the layer is effectively arranged at the organic conductive polymer film such as polypyrrole and the bonding interface between the dielectric oxide film and the organic conductive polymer film, and the polypyrrole layer. Since it is restored with a small amount of energy, polypyrrole can be prevented from decomposing and graphitizing, reducing the capacitance and ESR.
The solid electrolytic capacitor with uniform characteristics can be manufactured without increasing In addition, it does not use a substance that deteriorates the characteristics such as a surfactant, and does not require a step of forming an organic conductive polymer film by electrolytic oxidation polymerization. Can be formed.
【００１１】[0011]
【実施例】以下、本発明について、図面を参照して説明
する。従来例と同一部分には同一参照符号を付して説明
を省略する。図１に示すように、中央部にタンタルリー
ド１を植立したタンタル焼結体２をリン酸水溶液中で９
０Ｖで陽極酸化し、洗浄、乾燥して五酸化タンタルの誘
電体皮膜３を形成したペレットを得る。ついで、このペ
レットを２０ｗｔ％のドデシベルスルフォン酸第二鉄塩
のメタノール溶液に浸漬し、乾燥後、１００％のピロー
ル溶液に浸漬し、化学酸化重合して導電性ポリピロール
層４を形成する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. The same parts as those of the conventional example are designated by the same reference numerals and the description thereof will be omitted. As shown in FIG. 1, the tantalum sintered body 2 in which the tantalum lead 1 was planted in the center was placed in a phosphoric acid aqueous solution.
Anodization is performed at 0 V, washing and drying are performed to obtain pellets on which tantalum pentoxide dielectric film 3 is formed. Next, the pellets are dipped in a 20 wt% ferric dodecyl sulfonic acid methanol solution, dried and then dipped in a 100% pyrrole solution, and chemically oxidized and polymerized to form the conductive polypyrrole layer 4.
【００１２】ついで、図２に示すように、有機溶剤例え
ばメタノールとリン酸との混合液中のリン酸濃度が０．
００１〜１．０ｗｔ％となるようにメタノールにリン酸
を加えた混合液１２中でタンタルリード１を正、混合液
１２を負に接続し、電解処理を実施する、その後、従来
例と同様に、リン酸液中で電解処理を実施して、乾燥
後、ポリピロール層４の表面にグラファイト層５、銀ペ
ースト層６を塗布形成してコンデンサ素子を得る。そし
て、外部導出リード７、８をそれぞれタンタルリード１
および銀ペースト層６に接続し、樹脂９で外装して固体
電解コンデンサ１３が得られる。Then, as shown in FIG. 2, the concentration of phosphoric acid in the mixed solution of an organic solvent such as methanol and phosphoric acid is 0.
The tantalum lead 1 is connected to the positive side and the mixed solution 12 is connected to the negative side in the mixed solution 12 in which phosphoric acid is added to methanol so that the concentration becomes 001 to 1.0 wt%, and then electrolytic treatment is performed. Then, electrolytic treatment is carried out in a phosphoric acid solution, and after drying, a graphite layer 5 and a silver paste layer 6 are formed by coating on the surface of the polypyrrole layer 4 to obtain a capacitor element. Then, the externally derived leads 7 and 8 are respectively connected to the tantalum lead 1
Then, the solid electrolytic capacitor 13 is obtained by connecting to the silver paste layer 6 and covering with the resin 9.
【００１３】このように、本発明の製造方法により製造
した固体電解コンデンサ１３と、従来の製造方法、すな
わちメタノールとリン酸の混合液中での電解処理を実施
しないで製造したものとの特性測定を行なった結果、図
３乃至図５に示すように、Ｔａｎδ、ＥＳＲ、リーク電
流（ＬＣ）の各特性において、従来の製造方法によるも
のはＨＨ，ＬＨの２製造ロットともに、極端に各測定値
が大きいものが発生しているのに対し、本発明の製造方
法によると、ＨＭＨ，ＬＭＨの２製造ロットともに、各
測定値が極端に大きいものがなく、均一な特性の固体電
解コンデンサが得られていることが判る。As described above, the characteristic measurement of the solid electrolytic capacitor 13 manufactured by the manufacturing method of the present invention and the conventional manufacturing method, that is, the one manufactured without performing the electrolytic treatment in the mixed solution of methanol and phosphoric acid. As a result, as shown in FIG. 3 to FIG. 5, in each characteristic of Tan δ, ESR, and leakage current (LC), the values measured by the conventional manufacturing method are extremely high in the two measured lots of HH and LH. However, according to the manufacturing method of the present invention, there is no extremely large measured value in each of the two manufacturing lots of HMH and LMH, and a solid electrolytic capacitor having uniform characteristics can be obtained. You can see that
【００１４】ここで、リン酸濃度が０．００１ｗｔ％未
満では液抵抗が高く、ペレットに十分な電圧が印加され
ないため、処理不足が生じる。また、１．０ｗｔ％を越
えると液電導度が高くなりすぎるため、ポリピロール層
に大きなエネルギーが加わり、グラファイト化等が起こ
り、ｔａｎＳ、ＥＳＲ特性が劣化する。以上、弁作用を
有する金属としてタンタルを使用し、有機導電性高分子
材料としてポリピロールを用い、有機溶剤としてメタノ
ールを用いた例について説明したが、本発明は上記例に
限定されず、弁作用を有する金属としてアルミニウムを
使用し、有機導電性高分子材料としてポリピロール、ポ
リチオフェン、ポリフランを含む環状化合物および該環
状化合物の誘導体の群から選ばれた一種を用い、有機溶
剤として上記有機導電性高分子化合物を溶解しないも
の、例えばエタノール、エチレングリコール、ジメチル
ホルムアミド、プロピレンカーボネート、γ−プチロラ
クトン等のアルコール系溶剤を使用しても同様な効果が
得られる。Here, if the phosphoric acid concentration is less than 0.001 wt%, the liquid resistance is high and a sufficient voltage is not applied to the pellets, resulting in insufficient treatment. On the other hand, if it exceeds 1.0 wt%, the liquid conductivity becomes too high, so that a large amount of energy is applied to the polypyrrole layer, graphitization and the like occur, and the tanS and ESR characteristics deteriorate. As described above, tantalum is used as a metal having a valve action, polypyrrole is used as an organic conductive polymer material, and an example in which methanol is used as an organic solvent has been described, but the present invention is not limited to the above example, and valve action is Using aluminum as a metal having, using one kind selected from the group of cyclic compounds containing polypyrrole, polythiophene, polyfuran and derivatives of the cyclic compound as an organic conductive polymer material, the organic conductive polymer compound as an organic solvent The same effect can be obtained by using a solvent which does not dissolve, for example, an alcohol solvent such as ethanol, ethylene glycol, dimethylformamide, propylene carbonate, or γ-ptyrolactone.
【００１５】また、実施例では本発明の有機溶剤とリン
酸との混合液中での電解処理の後に、従来と同様リン酸
水溶液中での電解処理を実施した例について説明した
が、このリン酸水溶液中での電解処理を省略することも
できる。In the examples, the electrolytic treatment in the mixed solution of the organic solvent of the present invention and phosphoric acid was followed by the electrolytic treatment in the phosphoric acid aqueous solution as in the conventional case. The electrolytic treatment in the acid aqueous solution can be omitted.
【００１６】[0016]
【発明の効果】本発明の製造方法にによれば、有機導電
性高分子と親和性の良好な有機溶剤とリン酸との混合液
中で有機導電性高分子層が電解処理されるため、化学酸
化重合で形成された有機導電性高分子層に注入されてい
るドデシベルスルフォン酸基等のドーパントがポリピロ
ール等の有機導電性高分子膜および誘電体酸化皮膜と有
機導電性高分子膜との接合界面に有効に配置されるとと
もに、ポリピロール層が小さいエネルギーで修復される
ため、静電容量の減少やＥＳＲの増加が生ぜず、均一な
特性の固体電解コンデンサを製造できる。また、界面活
性剤等の特性を劣化させる物質を使用しないため、電解
酸化重合による有機導電性高分子膜の形成工程も不要な
良質の有機導電性高分子膜の形成が可能となる。According to the production method of the present invention, since the organic conductive polymer layer is subjected to electrolytic treatment in a mixed solution of an organic solvent having a good affinity with the organic conductive polymer and phosphoric acid, The organic conductive polymer film such as polypyrrole and the organic conductive polymer film, such as polypyrrole, which is injected into the organic conductive polymer layer formed by the chemical oxidative polymerization, is doped with a dopant such as polypyrrole. Since the polypyrrole layer is effectively disposed at the bonding interface and the polypyrrole layer is restored with a small amount of energy, a solid electrolytic capacitor having uniform characteristics can be manufactured without causing a decrease in capacitance and an increase in ESR. In addition, since a substance such as a surfactant that deteriorates the characteristics is not used, it is possible to form a high-quality organic conductive polymer film that does not require the step of forming the organic conductive polymer film by electrolytic oxidation polymerization.
【図１】 本発明により製造した一実施例の固体電解コ
ンデンサの構成断面図FIG. 1 is a structural cross-sectional view of a solid electrolytic capacitor of an embodiment manufactured according to the present invention.
【図２】 本発明の一実施例の電解処理の概略図FIG. 2 is a schematic diagram of an electrolytic treatment according to an embodiment of the present invention.
【図３】 Ｔａｎδ特性の分布図FIG. 3 is a distribution diagram of Tan δ characteristics.
【図４】 ＥＳＲ特性の分布図FIG. 4 Distribution chart of ESR characteristics
【図５】 リーク電流（ＬＣ）特性の分布図FIG. 5 is a distribution diagram of leakage current (LC) characteristics
【図６】 従来の固体電解コンデンサの構成断面図FIG. 6 is a sectional view showing the structure of a conventional solid electrolytic capacitor.
【図７】 従来の他の固体電解コンデンサの構成断面図FIG. 7 is a sectional view showing the structure of another conventional solid electrolytic capacitor.
１ タンタルリード ２ 焼結体（陽極） ３ 誘電体酸化皮膜 ４ ポリピロール層（有機導電性高分子層） １２ 混合液 １３ 固体電解コンデンサ 1 Tantalum Lead 2 Sintered Body (Anode) 3 Dielectric Oxide Film 4 Polypyrrole Layer (Organic Conductive Polymer Layer) 12 Mixed Liquid 13 Solid Electrolytic Capacitor
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新居 真二 滋賀県大津市晴嵐２丁目９番１号 関西日 本電気株式会社内 (72)発明者 田中 義之 滋賀県大津市晴嵐２丁目９番１号 関西日 本電気株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shinji Arai, 2-9-1 Harashirashi, Otsu-shi, Shiga Kansai Nihon Electric Co., Ltd. (72) Inventor Yoshiyuki Tanaka 2--9-1 Harashirashi, Otsu, Shiga Prefecture Kansai Nippon Electric Co., Ltd.
Claims (3)
誘電体酸化皮膜を形成し、さらに、前記誘電体酸化皮膜
上に有機導電性高分子層を化学酸化重合で形成し、次い
で有機溶剤とリン酸とを混合した液を用いて電解処理
し、その後グラファイト層および導電ペースト層を順次
塗布して、陰極層を形成する固体電解コンデンサの製造
方法。1. A dielectric oxide film is formed on the surface of an anode made of a metal having a valve action, and an organic conductive polymer layer is formed on the dielectric oxide film by chemical oxidative polymerization, and then an organic solvent. A method for producing a solid electrolytic capacitor, which comprises electrolytically treating a mixed solution of a phosphoric acid and phosphoric acid, and then sequentially coating a graphite layer and a conductive paste layer to form a cathode layer.
ポリチオフェンまたはポリフランを含む環状化合物およ
び該環状化合物の誘導体の群から選ばれた一種で構成さ
れた層であり、前記有機溶剤がアルコール系溶剤である
ことを特徴とする請求項１記載の固体電解コンデンサの
製造方法。2. The organic conductive polymer layer is polypyrrole,
2. The solid electrolytic capacitor according to claim 1, wherein the solid electrolytic capacitor is a layer composed of one kind selected from the group of cyclic compounds containing polythiophene or polyfuran and derivatives of the cyclic compounds, and the organic solvent is an alcohol solvent. Manufacturing method.
度が０．００１ｗｔ％乃至１．０ｗｔ％であることを特
徴とする請求項１記載の固体電解コンデンサの製造方
法。3. The method for producing a solid electrolytic capacitor according to claim 1, wherein the phosphoric acid concentration of the mixed solution of the organic solvent and phosphoric acid is 0.001 wt% to 1.0 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19638794A JP2792441B2 (en) | 1994-08-22 | 1994-08-22 | Method for manufacturing solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19638794A JP2792441B2 (en) | 1994-08-22 | 1994-08-22 | Method for manufacturing solid electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0864476A true JPH0864476A (en) | 1996-03-08 |
| JP2792441B2 JP2792441B2 (en) | 1998-09-03 |
Family
ID=16357031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19638794A Expired - Fee Related JP2792441B2 (en) | 1994-08-22 | 1994-08-22 | Method for manufacturing solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2792441B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110235A (en) * | 1997-09-01 | 2000-08-29 | Nec Corporation | Fabrication method of solid electrolytic capacitor using organic conducting polymer |
| JP2011091413A (en) * | 2009-10-23 | 2011-05-06 | Avx Corp | External coating for solid electrolytic capacitor |
-
1994
- 1994-08-22 JP JP19638794A patent/JP2792441B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110235A (en) * | 1997-09-01 | 2000-08-29 | Nec Corporation | Fabrication method of solid electrolytic capacitor using organic conducting polymer |
| JP2011091413A (en) * | 2009-10-23 | 2011-05-06 | Avx Corp | External coating for solid electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2792441B2 (en) | 1998-09-03 |
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