JPH02249221A - Solid electrolytic capacitor - Google Patents
Solid electrolytic capacitorInfo
- Publication number
- JPH02249221A JPH02249221A JP1069198A JP6919889A JPH02249221A JP H02249221 A JPH02249221 A JP H02249221A JP 1069198 A JP1069198 A JP 1069198A JP 6919889 A JP6919889 A JP 6919889A JP H02249221 A JPH02249221 A JP H02249221A
- Authority
- JP
- Japan
- Prior art keywords
- polymer compound
- oxide film
- dielectric oxide
- conductive polymer
- solid electrolytic
- 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.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000011888 foil Substances 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 abstract description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 2
- 235000011037 adipic acid Nutrition 0.000 abstract 1
- 239000001361 adipic acid Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 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 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 150000001450 anions Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は固体電解コンデンサ、特に、固体電解質として
導電性高分子化合物を用いた固体電解コンデンサに関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a solid electrolytic capacitor, and particularly to a solid electrolytic capacitor using a conductive polymer compound as a solid electrolyte.
［従来の技術］
近年、電子機器の小型化、軽量化に伴って、高周波領域
におけるインピーダンスが低く、小型で大容量のコンデ
ンサが要求されるようになってきた。[Prior Art] In recent years, as electronic devices have become smaller and lighter, there has been a demand for small, large-capacity capacitors with low impedance in a high frequency range.
このような高周波用のコンデンサとしては従来、マイカ
コンデンサ、フィルムコンデンサ、セラミックコンデン
サなどが使用されているが、これらのコンデンサはいず
れも大容量化に適したものではない。Conventionally, mica capacitors, film capacitors, ceramic capacitors, etc. have been used as such high frequency capacitors, but none of these capacitors are suitable for increasing the capacity.
一方、小型で大容量のコンデンサとしては、アルミニウ
ム電解コンデンサやタンタルコンデンサなどがある。On the other hand, small-sized, large-capacity capacitors include aluminum electrolytic capacitors and tantalum capacitors.
アルミニウム電解コンデンサは低コストで大容量のもの
が得られるという利点はあるが、電解液を用いているた
めに経時的に電解液が蒸発することによる容量劣化があ
り、また高周波特性が悪いなど欠点があった。Aluminum electrolytic capacitors have the advantage of being able to provide large capacity at low cost, but because they use an electrolyte, their capacity deteriorates over time as the electrolyte evaporates, and they also have poor high frequency characteristics. was there.
一方、タンタル固体電解コンデンサは、電解質として固
体の二酸化マンガンなどを用いることによって容量劣化
などアルミニウム電解コンデンサの欠点を克服している
。しかしながら。On the other hand, tantalum solid electrolytic capacitors overcome the drawbacks of aluminum electrolytic capacitors, such as capacity deterioration, by using solid manganese dioxide or the like as an electrolyte. however.
この固体電解質は硝酸マンガン水溶液を弁作用金属体に
含浸・付着させた後、３５０℃前後で硝酸マンガンを熱
分解して形成され、二酸化マンガンの付着量を増加させ
るために通常数回ないし士数回の含浸・熱分解の工程を
繰り返す必要があるため、熱分解時に誘電体としての酸
化皮膜の損傷が発生したり、あるいは二酸化マンガン皮
膜の補修能力が低いなどの欠点があった。This solid electrolyte is formed by impregnating and adhering an aqueous solution of manganese nitrate to the valve metal body, and then thermally decomposing the manganese nitrate at around 350°C. Since it is necessary to repeat the impregnation and pyrolysis steps twice, there are drawbacks such as damage to the oxide film as a dielectric during pyrolysis and low repair ability of the manganese dioxide film.
そこでこれらの欠点を解消するため、特開昭５８−１７
６０９号公報などに、誘電体酸化皮膜の補修性が優れ、
かつ導電性の良好な有機固体電解質として、７．７．８
．８テトラシアノキノジメタン錯塩（以下、 ＴＣＮＱ
錯塩と略称する）を用いたものが提案されている。Therefore, in order to eliminate these drawbacks, Japanese Patent Laid-Open No. 58-17
609, etc., the dielectric oxide film has excellent repairability,
and as an organic solid electrolyte with good conductivity, 7.7.8
．． 8 tetracyanoquinodimethane complex salt (hereinafter referred to as TCNQ)
A method using complex salts (abbreviated as complex salts) has been proposed.
この特開昭５８−１７６０９号公報には、Ｎの位置をア
ルキル基で置換したイソキノリンとＴＣＮＱからなるＴ
ＣＮＱ錯塩を加熱・溶融してコンデンサ素子に含浸後、
冷却・固化することにより固体電解質層を形成したもの
が開示されている。またビロール等の複素五員環化合物
の重合体を固体電解質として用いることも提案されてい
る。（特開昭６０−３７１）４号公報参照）
［発明が解決しようとする課題］
しかしながら、このようなＴＣＮＱ錯塩を用いた固体電
解コンデンサにおいては、前記含浸後の冷却・固化の際
、ＴＣＮＱ錯塩が結晶化して誘電体酸化皮膜に充分密着
しないため、初期の静電容量が得られないという問題点
があった。JP-A-58-17609 discloses that TCNQ is composed of isoquinoline and TCNQ in which the N position is substituted with an alkyl group.
After heating and melting the CNQ complex salt and impregnating it into the capacitor element,
A solid electrolyte layer formed by cooling and solidifying is disclosed. It has also been proposed to use a polymer of a five-membered heterocyclic compound such as virol as a solid electrolyte. (Refer to Japanese Patent Application Laid-Open No. 60-371) No. 4) [Problems to be Solved by the Invention] However, in a solid electrolytic capacitor using such a TCNQ complex salt, during cooling and solidification after the impregnation, the TCNQ complex salt There was a problem in that the initial capacitance could not be obtained because it crystallized and did not adhere sufficiently to the dielectric oxide film.
また導電性高分子化合物を用いた固体電解コンデンサに
おいては、化学重合法を使用する場合、粉末状の導電性
高分子化合物が得られやすいため誘電体酸化皮膜に対す
る付着が強固な物が得られにくい、−刃型解重合で導電
性高分子化合物を形成する場合、絶縁性の誘電体酸化皮
膜上に電解重合を行うため均一な導電性高分子化合物が
形成されにく（十分な容量が得られないという問題点が
あった。In addition, for solid electrolytic capacitors using conductive polymer compounds, when chemical polymerization is used, it is easy to obtain a powdered conductive polymer compound, making it difficult to obtain a solid electrolytic capacitor that adheres strongly to the dielectric oxide film. , - When forming a conductive polymer compound by blade-type depolymerization, it is difficult to form a uniform conductive polymer compound because electrolytic polymerization is performed on an insulating dielectric oxide film (sufficient capacity cannot be obtained). The problem was that there was no.
［課題を解決する為の手段］
本発明者は、前述の諸問題点を解決することを目的とし
て種々研究、検討した結果、誘電体酸化皮膜に対する導
電性高分子化合物の接着性を改善せしめることにより前
記目的を達成し得ることを見出した。[Means for Solving the Problems] As a result of various studies and examinations aimed at solving the above-mentioned problems, the present inventor has found that the adhesiveness of a conductive polymer compound to a dielectric oxide film can be improved. It has been found that the above object can be achieved.
か（して本発明は、導電性高分子化合物を誘電体酸化皮
膜上に設けた固体電解コンデンサにおいて、誘電体酸化
皮膜を予め高分子化合物により導電性を損わない様に被
覆し、更にこの上に導電性高分子化合物を形成せしめた
固体電解コンデンサを提供するにある。(Thus, the present invention provides a solid electrolytic capacitor in which a conductive polymer compound is provided on a dielectric oxide film, in which the dielectric oxide film is coated in advance with a polymer compound so as not to impair conductivity, and The present invention provides a solid electrolytic capacitor having a conductive polymer compound formed thereon.
本発明に用いられる導電性高分子化合物としては、π電
子共役系を有する高分子化合物のことであり、高い伝導
度と安定性を有する複素五員環化合物、とりわけ重合の
容易さからポリピロール、ポリチオフェン、ポリフラン
及びその誘導体が好ましい。The conductive polymer compound used in the present invention is a polymer compound having a π-electron conjugated system, and includes five-membered heterocyclic compounds with high conductivity and stability, especially polypyrrole and polythiophene because of their ease of polymerization. , polyfuran and its derivatives are preferred.
又１本発明に用いられる誘電体酸化皮膜を導電性を損わ
ない様に被覆せしめる高分子化合物としては、導電性高
分子化合物に平滑性及び加工性を付与するものとして少
なくとも一柿の溶媒に可溶であるものが望ましい。In addition, as a polymer compound used in the present invention to coat the dielectric oxide film without impairing conductivity, at least one persimmon solvent is used as a material that imparts smoothness and processability to the conductive polymer compound. Preferably, it is soluble.
具体的には、イオン交換性を有する高分子化合物、とり
わけスルホン酸やカルボン酸等の陽イオン交換基を持ち
、固定ドーパントとして導電性高分子化合物にドープさ
れ得るものとして含弗素陽イオン交換樹脂、ポリスチレ
ンスルホン酸、ポリビニルスルホン酸が挙げられる。Specifically, polymer compounds having ion exchange properties, particularly fluorine-containing cation exchange resins having cation exchange groups such as sulfonic acid and carboxylic acid, and which can be doped into conductive polymer compounds as fixed dopants, Examples include polystyrene sulfonic acid and polyvinyl sulfonic acid.
又、導電性高分子化合物と化学的結合を生じず、中に混
合するが如くして複合構造を採るものとしてポリ塩化ビ
ニル、ポリカーボネート。Also, polyvinyl chloride and polycarbonate are compounds that do not form chemical bonds with conductive polymer compounds, but can be mixed into them to form a composite structure.
ポリビニルアルコール、ポリビニルブチラール、ポリビ
ニルカルバゾール、ポリエチレングリコール及びその誘
導体が挙げられる。Examples include polyvinyl alcohol, polyvinyl butyral, polyvinyl carbazole, polyethylene glycol and derivatives thereof.
これら高分子化合物はイオン交換基を有する高分子化合
物はそれ自体導電性を有するものの、導電性を損わない
ように誘電体酸化皮膜−にに被覆せしめる必要−Ｊ：、
、一般に膜厚として０．０１〜３０μ程度に被覆せしめ
るのが適当である。Although these polymer compounds have ion exchange groups and are conductive in themselves, they need to be coated with a dielectric oxide film so as not to impair the conductivity.
Generally, it is appropriate to coat the film with a thickness of about 0.01 to 30 μm.
かくしてこの様な高分子化合物が被覆された誘電体酸化
皮膜には、前述の導電性高分子化合物が設けられる。Thus, the dielectric oxide film coated with such a polymer compound is provided with the above-mentioned conductive polymer compound.
かかる導電性高分子化合物層の形成方法としては、公知
の化学重合法や電解重合法が使用出来る。化学重合法と
しては、導電性高分子化合物の単量体を高分子化合物層
に含浸後、それをドーパントとなるアニオンと、酸化剤
とを含む溶液中に浸漬することで形成出来る。又、予め
高分子層に酸化剤とドーパントとなるアニオンを含む溶
液を含浸後、導電性高分子化合物の単量体含有溶液に浸
漬することも出来る。As a method for forming such a conductive polymer compound layer, a known chemical polymerization method or electrolytic polymerization method can be used. As a chemical polymerization method, it can be formed by impregnating a polymer compound layer with a monomer of a conductive polymer compound, and then immersing it in a solution containing an anion serving as a dopant and an oxidizing agent. Alternatively, the polymer layer can be impregnated in advance with a solution containing an oxidizing agent and an anion serving as a dopant, and then immersed in a solution containing a monomer of a conductive polymer compound.
電解重合法としては、例えば導電性高分子化合物の単量
体とドーパントとなるアニオンを溶解した電解液に、高
分子化合物で被覆された誘電体酸化皮膜体（陽極アルミ
ニウム箔）をアノードとして電解することにより、電気
化学的にドーピングされた導電性高分子化合物層を形成
せしめることが出来る。In the electrolytic polymerization method, for example, electrolysis is performed using a dielectric oxide film (anode aluminum foil) coated with a polymer compound as an anode in an electrolytic solution in which a monomer of a conductive polymer compound and an anion as a dopant are dissolved. By this, an electrochemically doped conductive polymer compound layer can be formed.
［実施例］
以下実施例、比較例をあげて本発明をさらに詳細に説明
する。[Example] The present invention will be explained in more detail with reference to Examples and Comparative Examples below.
実施例１．化成処理により表面に誘電体酸化皮膜を形成
させたアルミニウム陽極箔に高分子化合物としてスルホ
ン酸含有パーフルオロビニルエーテルとテトラフルオロ
エチレンとの共重合体（旭硝子社製商品名フレミオン）
のエタノール溶液を塗布後乾燥した。電解液として０．
２ｍ。Example 1. Copolymer of sulfonic acid-containing perfluorovinyl ether and tetrafluoroethylene as a polymer compound on aluminum anode foil with dielectric oxide film formed on the surface by chemical conversion treatment (product name: Flemion, manufactured by Asahi Glass Co., Ltd.)
After applying the ethanol solution, it was dried. 0 as electrolyte.
2m.
１７氾のビロールと０． ｌ ｍｏｌ ／ Ｒ，のナフ
タレンスルホン酸を含む水溶液を用い、白金板を陰極と
して電流密度０．５ｍＡ ／ ｃｍ”で２時間定電流電
解した。反応路ｒ後アジピン酸化成液にて再化成した。17 Flood Viror and 0. Using an aqueous solution containing 1 mol/R of naphthalene sulfonic acid, constant current electrolysis was carried out for 2 hours at a current density of 0.5 mA/cm'' using a platinum plate as a cathode.After the reaction path r, reconstitution was performed with an adipine oxidation solution.
次に陽極箔上に生成した導電性高分子化合物にカーボン
ペーストと銀ペーストを塗布し対極リードを取り出した
後、エポキシ樹脂により外装して固体電解コンデンサを
作製した。得られたコンデンサの特性を第１表に示す。Next, carbon paste and silver paste were applied to the conductive polymer compound formed on the anode foil, the counter electrode lead was taken out, and the solid electrolytic capacitor was then packaged with epoxy resin. Table 1 shows the characteristics of the obtained capacitor.
実施例２．実施例１と同じ陽極箔にポリスチレンスルホ
ン酸の水溶液を塗布後乾燥した。電解液として０．２ｍ
ｏｌ／ Ｑのビロールと０．１ｒａｏｌ／ Ｑのトルエ
ンスルホン酸を含むアセトニトリル溶液を用い、白金板
を陰極として電流密度０．５１＾／ｃｒａ”で２時間定
電流電解した０次に実施例１と同様の処理をして固体電
解コンデンサを作製した。得られたコンデンサの特性を
第１表に示す。Example 2. An aqueous solution of polystyrene sulfonic acid was applied to the same anode foil as in Example 1 and then dried. 0.2m as electrolyte
Using an acetonitrile solution containing virol of ol/Q and toluenesulfonic acid of 0.1 raol/Q, constant current electrolysis was carried out for 2 hours at a current density of 0.51^/cra'' using a platinum plate as a cathode.Next, Example 1 and A solid electrolytic capacitor was produced in the same manner.The characteristics of the obtained capacitor are shown in Table 1.
実施例３．実施例１と同じ陽極箔にポリカーボネートの
ジメチルホルムアミド溶液を塗布後乾燥した。電解液と
して０．２ｍｏｌ／βのビロールと０、 ｌａ＋ｏ１．
／ １２のベンゼンスルホン酸を含む水溶液を用い、白
金板を陰極として電流密度０．５ｒａＡ ／Ｃ１）２で
２時間定電流電解した１次に実施例１と同様の処理をし
て固体電解コンデンサを作製した。得られたコンデンサ
の特性を第１表に示す６
実施例４．実施例１と同じ陽極箔にポリビニルアルコー
ルの水溶液を塗布後乾燥した。電解液として０．２ｗｏ
ｌ／ｆｆのビロールと０．１ｍｏｌ／ｆｆのトルエンス
ルホン酸を含むメタノール溶液を用い、白金板を陰極と
して電流密度０．５ｍＡ ／ ｃｒｓ”で２時間定電流
電解した１次に実施例１と同様の処理をして固体電解コ
ンデンサを作製した。Example 3. A dimethylformamide solution of polycarbonate was applied to the same anode foil as in Example 1 and then dried. As an electrolyte, 0.2 mol/β of virol and 0, la+o1.
1. Using an aqueous solution containing benzenesulfonic acid of /12, constant current electrolysis was carried out for 2 hours at a current density of 0.5 raA /C1)2 using a platinum plate as a cathode.Next, the same treatment as in Example 1 was carried out to form a solid electrolytic capacitor. Created. The characteristics of the obtained capacitor are shown in Table 1.6 Example 4. An aqueous solution of polyvinyl alcohol was applied to the same anode foil as in Example 1 and then dried. 0.2wo as electrolyte
A methanol solution containing l/ff of virole and 0.1 mol/ff of toluenesulfonic acid was used to perform constant current electrolysis for 2 hours at a current density of 0.5 mA/crs with a platinum plate as a cathode.The same as in Example 1. A solid electrolytic capacitor was fabricated by the above treatment.
得られたコンデンサの特性を第１表に示す。Table 1 shows the characteristics of the obtained capacitor.
比較例１．実施例１と同じ陽極箔を使用し、電解液とし
て０．２ｇ＋ｏｌ／１２のビロールとＯ，１ｍｋｌ／ｆ
ｆのトルエンスルホン酸を含む水溶液を用い、白金板を
陰極として電流密度０．５ ｍＡ／ｃｍ”で２時間定電
流電解した０次に実施例１と同様の処理をして固体電解
コンデンサを作製した。得られたコンデンサの特性を第
１表に示す。Comparative example 1. The same anode foil as in Example 1 was used, and the electrolyte was 0.2 g + ol/12 virol and O, 1 mkl/f.
Using an aqueous solution containing toluenesulfonic acid f, constant current electrolysis was carried out for 2 hours at a current density of 0.5 mA/cm'' using a platinum plate as a cathode.Next, the same treatment as in Example 1 was carried out to produce a solid electrolytic capacitor. Table 1 shows the characteristics of the obtained capacitor.
第 １
表
［発明の効果］
本発明によるコンデンサは、誘電体酸化皮膜への接着性
が良くかつ平滑な導電性高分子化合物を形成することが
可能となる。したがって重合後の再化成処理によっても
導電性高分子化合物が誘電体酸化皮膜より脱落すること
もない。Table 1 [Effects of the Invention] In the capacitor according to the present invention, it is possible to form a conductive polymer compound that has good adhesion to a dielectric oxide film and is smooth. Therefore, the conductive polymer compound does not fall off from the dielectric oxide film even during reconversion treatment after polymerization.
このように本発明により容量が高く、等価直列抵抗が低
くかつ漏れ電流が低い固体電解コンデンサを提供するこ
とができる。As described above, the present invention can provide a solid electrolytic capacitor with high capacity, low equivalent series resistance, and low leakage current.
Claims (7)
体電解コンデンサにおいて、誘電体酸化皮膜を予め高分
子化合物により導電性を損なわない様に被覆し、更にこ
の上に導電性高分子化合物を形成せしめた固体電解コン
デンサ。1. In solid electrolytic capacitors in which a conductive polymer compound is provided on a dielectric oxide film, the dielectric oxide film is coated with a polymer compound in advance so as not to impair conductivity, and then a conductive polymer compound is formed on top of this. Solid electrolytic capacitor.
る高分子化合物が、イオン交換性を有する高分子化合物
である請求項（１）のコンデンサ。2. 2. The capacitor according to claim 1, wherein the polymer compound provided on the dielectric oxide film so as not to impair conductivity is a polymer compound having ion exchange properties.
ン交換体である請求項（２）のコンデンサ。3. 3. The capacitor according to claim 2, wherein the polymer compound having ion exchange properties is a fluorine-containing ion exchanger.
スルホン酸、ポリビニルスルホン酸及びこれらの誘電体
である請求項（２）のコンデンサ。4. 3. The capacitor according to claim 2, wherein the polymer compound having ion exchange properties is polystyrene sulfonic acid, polyvinyl sulfonic acid, or a dielectric thereof.
る高分子化合物が、ポリ塩化ビニ ル、ポリカーボネート、ポリビニルアルコール、ポリビ
ニルブチラール、ポリビニルカルバゾール、ポリエチレ
ングリコールである請求項（１）のコンデンサ。5. 2. The capacitor according to claim 1, wherein the polymer compound provided on the dielectric oxide film so as not to impair conductivity is polyvinyl chloride, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyvinyl carbazole, or polyethylene glycol.
ン、ポリフラン及びこれらの誘導体である請求項（１）
のコンデンサ。6. Claim (1) wherein the conductive polymer compound is polypyrrole, polythiophene, polyfuran, or a derivative thereof.
capacitor.
が電解重合法である請求項（１）のコンデンサ。7. 2. The capacitor according to claim 1, wherein the means for forming the conductive polymer compound on the polymer compound is an electrolytic polymerization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069198A JPH02249221A (en) | 1989-03-23 | 1989-03-23 | Solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069198A JPH02249221A (en) | 1989-03-23 | 1989-03-23 | Solid electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02249221A true JPH02249221A (en) | 1990-10-05 |
Family
ID=13395794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1069198A Pending JPH02249221A (en) | 1989-03-23 | 1989-03-23 | Solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02249221A (en) |
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| JP2006100774A (en) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | Capacitor and its manufacturing method |
| WO2006068302A1 (en) * | 2004-12-24 | 2006-06-29 | Showa Denko K.K. | Solid electrolytic capacitor element, solid electrolytic capacitor and method for manufacturing same |
| US7423862B2 (en) | 2004-12-24 | 2008-09-09 | Showa Denko K.K. | Solid electrolytic capacitor element, solid electrolytic capacitor and production method thereof |
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1989
- 1989-03-23 JP JP1069198A patent/JPH02249221A/en active Pending
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|---|---|---|---|---|
| JP2007532359A (en) * | 2004-04-13 | 2007-11-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive polymer composite |
| WO2005100473A1 (en) * | 2004-04-13 | 2005-10-27 | E.I. Dupont De Nemours And Company | Conductive polymer composites |
| US8147962B2 (en) | 2004-04-13 | 2012-04-03 | E. I. Du Pont De Nemours And Company | Conductive polymer composites |
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| JP2006100774A (en) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | Capacitor and its manufacturing method |
| US8551366B2 (en) | 2004-08-30 | 2013-10-08 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium |
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| WO2006068302A1 (en) * | 2004-12-24 | 2006-06-29 | Showa Denko K.K. | Solid electrolytic capacitor element, solid electrolytic capacitor and method for manufacturing same |
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| US8216680B2 (en) | 2006-02-03 | 2012-07-10 | E I Du Pont De Nemours And Company | Transparent composite conductors having high work function |
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