JPH10261417A - Organic polymer thin film electrode and its manufacture - Google Patents
Organic polymer thin film electrode and its manufactureInfo
- Publication number
- JPH10261417A JPH10261417A JP9063074A JP6307497A JPH10261417A JP H10261417 A JPH10261417 A JP H10261417A JP 9063074 A JP9063074 A JP 9063074A JP 6307497 A JP6307497 A JP 6307497A JP H10261417 A JPH10261417 A JP H10261417A
- Authority
- JP
- Japan
- Prior art keywords
- organic polymer
- thin film
- electrode
- film
- film electrode
- Prior art date
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電池、素子、電気分
解に用いることができる有機高分子膜からなる薄膜電極
及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery, a device, a thin film electrode comprising an organic polymer film which can be used for electrolysis, and a method for producing the same.
【０００２】[0002]
【従来の技術】例えば、導電性基材上に芳香族有機高分
子薄膜などのような有機高分子薄膜を形成した電極は、
通常の金属電極にはない３次元的な構造を有しており、
その中に種々の触媒や導電性物質、光応答性材料を取り
込める性質があるため、新規な機能性材料として注目さ
れている（高分子機能電極、高分子学会編、１９８３、
学会出版センター刊、第３章、ｐ．３９、第５章、ｐ．
９５、第６章、ｐ．１１７）。現在では、このような種
類の電極は、ポリマー電池材料、電子デバイスとしての
エレクトロクロミズム素子、選択性を生かしたセンサ
ー、電解合成用電極材料などへの利用が盛んに行われて
いる。有機ポリマー電池では従来の無機系電池に比較し
て格段に軽量化できることが報告されている（日本化学
会、化学と工業、１９９６、第４９巻、１２号、ｐ．１
６４３）。2. Description of the Related Art For example, an electrode in which an organic polymer thin film such as an aromatic organic polymer thin film is formed on a conductive substrate,
It has a three-dimensional structure not found in ordinary metal electrodes,
Among them, it has the property of being able to incorporate various catalysts, conductive substances, and photoresponsive materials, and is attracting attention as a novel functional material (Polymer Functional Electrode, edited by The Society of Polymer Science, 1983,
Published by Gakkai Shuppan Center, Chapter 3, p. 39, Chapter 5, p.
95, Chapter 6, p. 117). At present, these types of electrodes are actively used for polymer battery materials, electrochromic elements as electronic devices, sensors utilizing selectivity, electrode materials for electrolytic synthesis, and the like. It has been reported that organic polymer batteries can be significantly reduced in weight compared to conventional inorganic batteries (The Chemical Society of Japan, Chemistry and Industry, 1996, Vol. 49, No. 12, p. 1).
643).
【０００３】このような有機高分子薄膜電極は、いずれ
の用途においても有機高分子薄膜の均一性、特性が安定
していることが期待されている。製法としては、原料で
あるモノマー（重合により有機高分子を形成し得る有機
化合物）を溶解した電解液に基材を陽極として浸漬し、
適当な電流を付加する。電解条件を決めることにより、
ある程度再現性のある薄膜が得られているが、機械的強
度、構造の均一性の面では不十分な面があり、特に低密
度であることは致命的であり、これを改善する必要があ
った。[0003] Such an organic polymer thin film electrode is expected to have stable organic polymer thin film uniformity and characteristics in any application. As a production method, the base material is immersed in an electrolytic solution in which a monomer (an organic compound capable of forming an organic polymer by polymerization) as a raw material is dissolved,
Appropriate current is applied. By determining the electrolysis conditions,
Although a reproducible thin film has been obtained to some extent, it has insufficient mechanical strength and structural uniformity, and particularly low density is fatal and needs to be improved. Was.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前述した従
来技術の種々の問題点を解消し、高密度で均一性の高い
有機高分子薄膜電極とその製造方法を提供することを目
的とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned various problems of the prior art and to provide a high-density, highly uniform organic polymer thin film electrode and a method for producing the same. .
【０００５】[0005]
【問題を解決するための手段】本発明の特徴を分かり易
く述べると、つぎのようになる。 １）導電性基材の上に有機高分子の薄膜を形成するため
に、超音波を照射しながら電気化学的に有機高分子の薄
膜を形成した電解重合膜電極であり、 ２）導電性基材の上に有機高分子の薄膜を形成するため
に、超音波を照射しながら電気化学的にこれを行うこと
を特徴とする電解重合膜の製造方法である。具体的に
は、 ３）電解重合物がポリアニリン、ポリフェノールあるい
はポリピロールであり、その厚さが０．００１〜１ｍｍ
であり、 ４）５ｋＨｚ〜１００ｋＨｚの超音波を照射することを
特徴とする製造方法である。金属の電気メッキでは超音
波を照射することにより、良好なメッキ層の得られるこ
とは知られているが、有機高分子薄膜電極では先例はな
い。SUMMARY OF THE INVENTION The features of the present invention will be described in the following. 1) an electropolymerized membrane electrode formed by electrochemically forming an organic polymer thin film while irradiating ultrasonic waves to form an organic polymer thin film on a conductive substrate; This is a method for producing an electrolytic polymerized film, which comprises electrochemically performing irradiation with ultrasonic waves to form a thin film of an organic polymer on a material. Specifically, 3) the electrolytic polymer is polyaniline, polyphenol or polypyrrole, and its thickness is 0.001 to 1 mm
And 4) irradiating ultrasonic waves of 5 kHz to 100 kHz. It is known that a good plating layer can be obtained by irradiating ultrasonic waves in metal electroplating, but there is no precedent for an organic polymer thin film electrode.
【０００６】[0006]
【発明の実施の形態】以下にその具体的製造方法の一例
を示す。図１は本電極の製作セルの一例を示すもので、
縦断面図を示している。導電性基材として厚さ０．１ｍ
ｍの白金板２上に厚さ０．０１ｍｍのポリアニリン薄膜
３を形成した有機高分子薄膜電極１を示す。電極基体と
する導電性基材としては、白金、チタン、ニオブ、タン
タル、ステンレス鋼、ニッケル、ジルコニウム、カーボ
ン、銀などの耐食性を有する板、金網、それらの粉末か
ら成る焼結体、金属繊維焼結体、発泡体等の多孔性材料
を用いることができる。対極には安定な白金、銅、銀、
ニッケルなどの板を用いる。電気化学的処理する際に
は、前処理としてその表面を脱脂、研磨することが好ま
しい。DESCRIPTION OF THE PREFERRED EMBODIMENTS An example of a specific manufacturing method will be described below. FIG. 1 shows an example of a production cell of the present electrode.
It shows a longitudinal section. 0.1m thickness as conductive substrate
1 shows an organic polymer thin film electrode 1 in which a 0.01 mm thick polyaniline thin film 3 is formed on a platinum plate 2 of m. Examples of the conductive base material used as the electrode base include a plate, a wire net, a sintered body made of the powder, a sintered body made of the powder, a metal fiber sintered body, such as platinum, titanium, niobium, tantalum, stainless steel, nickel, zirconium, carbon and silver. A porous material such as a binder or a foam can be used. The opposite pole is stable platinum, copper, silver,
A plate made of nickel or the like is used. When performing the electrochemical treatment, it is preferable that the surface is degreased and polished as a pretreatment.
【０００７】安定性、経済性の観点から、電気化学的処
理用（電解重合用）の電解液としては、目的の高分子の
原料であるモノマーを０．０１〜１Ｍ、電解質として適
宜に酸、塩基、塩を０．０５〜１０Ｍ、モノマーが水に
不溶である場合は適宜に極性有機溶媒を加えて調製す
る。適度に攪拌しながら電解重合させる。この間、電極
電位を反応が進行できる電位に保持するか、或いは電位
を繰り返し掃引することが好ましい。この「電位を繰り
返し掃引する」とは、電位を高い値から低い値（最低は
０）に順次低下させ、再び高い値に順次戻し、この変動
を繰り返すことをいう。このとき超音波発生端子を挿入
し発振させておく。振動数、エネルギー出力としては、
製造条件下においてキャビテーションが生起するように
選択する。その超音波の周波数としては、５ｋＨｚ〜１
００ｋＨｚの範囲とすることが好ましい。電解後は生成
した電解重合膜を溶媒で十分に洗浄する。From the viewpoints of stability and economy, the electrolytic solution for electrochemical treatment (for electrolytic polymerization) contains 0.01 to 1M of a monomer which is a raw material of a target polymer, and an acid, When the base and the salt are 0.05 to 10M and the monomer is insoluble in water, it is prepared by appropriately adding a polar organic solvent. Electropolymerize with moderate stirring. During this time, it is preferable to maintain the electrode potential at a potential at which the reaction can proceed, or to repeatedly sweep the potential. The term “repeatedly sweeping the potential” means that the potential is sequentially reduced from a high value to a low value (the minimum is 0), and then returned to a high value again, and this change is repeated. At this time, the ultrasonic generating terminal is inserted and oscillated. As frequency and energy output,
The choice is made so that cavitation occurs under the manufacturing conditions. The frequency of the ultrasonic wave is 5 kHz to 1
It is preferable to be in the range of 00 kHz. After the electrolysis, the formed electropolymerized film is sufficiently washed with a solvent.
【０００８】本発明による有機高分子薄膜の密度を測定
したところ、超音波を照射しない場合に比較して１０倍
以上の値となり、配向が整っているため透過性も向上す
ることが観察された。配向性が改善される理由としては
十分に解明されていないため不明な点があるが、超音波
によりモノマーが緻密に重なり合い、同一方向に規則正
しく重合反応が進行するのであると推定される。本発明
による電気化学的処理においては電解重合が行われる
が、その反応は電解酸化に伴って重合が行われるため
に、その重合により生成する有機高分子としては、一般
的には芳香族有機高分子であり、酸化部位を有するもの
であって、この点から本発明においては芳香族有機酸化
高分子が生成しているものが好ましい。本発明により得
られる有機高分子薄膜としては、ポリアニリン、ポリフ
ェノール、ポリピロール、ポリチオフェン、ポリフェニ
レンビニレン、ポリフェニレンアセチレン、ポリアセチ
レンなどの薄膜が挙げられ、このうち、好ましくはポリ
アニリン、ポリフェノール、ポリピロールの薄膜が挙げ
られる。When the density of the organic polymer thin film according to the present invention was measured, the density was 10 times or more as compared with the case where no ultrasonic wave was irradiated, and it was observed that the transmittance was improved because the orientation was adjusted. . The reason why the orientation is improved has not been sufficiently elucidated, and thus there is no known point. However, it is presumed that the monomers are densely overlapped by ultrasonic waves and the polymerization reaction proceeds regularly in the same direction. In the electrochemical treatment according to the present invention, electrolytic polymerization is carried out. Since the reaction is carried out in conjunction with electrolytic oxidation, the organic polymer produced by the polymerization is generally an aromatic organic polymer. It is a molecule having an oxidized site, and in this respect, a molecule in which an aromatic organic oxidized polymer is generated is preferable in the present invention. Examples of the organic polymer thin film obtained by the present invention include thin films of polyaniline, polyphenol, polypyrrole, polythiophene, polyphenylenevinylene, polyphenyleneacetylene, polyacetylene, and the like, and among them, thin films of polyaniline, polyphenol, and polypyrrole are preferable.
【０００９】[0009]
【実施例】以下、実施例により本発明を具体的に説明す
る。ただし、本発明はこれらの実施例のみに限定される
ものではない。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to only these examples.
【００１０】実施例１ 厚さ０．１ｍｍで高さ、幅が１ｃｍの白金製の板を基体
とし、前処理として表面を脱脂後、０．５ミクロンのア
ルミナ研磨剤で研磨した。この白金板を陽極として用
い、対極にも同様な白金板を用いた。電極間距離を２ｃ
ｍとした。電解液としてはアニリン０．１Ｍ、電解質と
して塩酸４Ｍを用いる。適度に攪拌しながら、電極電位
を０．０〜１．０Ｖ（ｖｓ．ＳＣＥ電位基準）の範囲に
保ちながら、０．１Ｖ／ｓｅｃ．の速度で繰り返し掃引
を５０回行った。このとき電極から１ｃｍ離れた位置に
超音波発生端子を掃引し発振させた。振動数としては、
２０ｋＨｚ、エネルギー出力としては７Ｗであった。終
了後の分析では厚さとしては５ミクロンで良好な均一性
及び高密度の薄膜が得られた。電解後はアセトンで十分
に洗浄した。電流電位曲線から求められる電気化学的な
活性容量は３．８×１０-3Ａ／ｃｍ2 であった。この電
解重合により得られたポリアニリン薄膜の密度を測定し
たところ、０．１ｇ／ｃｍ3 であり、超音波を照射しな
い場合に比較して１０倍の値となり、ほぼ理論的に予想
される密度となった。配向が整っているため透過性も向
上することが観察された。前記薄膜の密度としては、理
論的には１０％の充実率であった。Example 1 A platinum plate having a thickness of 0.1 mm, a height and a width of 1 cm was used as a substrate, and the surface was degreased as a pretreatment, and then polished with a 0.5 micron alumina abrasive. This platinum plate was used as an anode, and a similar platinum plate was used as a counter electrode. 2c distance between electrodes
m. Aniline 0.1 M is used as an electrolyte, and 4 M hydrochloric acid is used as an electrolyte. While maintaining the electrode potential in the range of 0.0 to 1.0 V (vs. SCE potential reference) with appropriate stirring, 0.1 V / sec. The sweep was repeated 50 times at a speed of. At this time, the ultrasonic wave generating terminal was swept to a position 1 cm away from the electrode and oscillated. As the frequency,
20 kHz and energy output was 7 W. After the analysis, a thin film with good uniformity and high density was obtained with a thickness of 5 microns. After the electrolysis, it was sufficiently washed with acetone. The electrochemically active capacity determined from the current-potential curve was 3.8 × 10 −3 A / cm 2 . When the density of the polyaniline thin film obtained by this electrolytic polymerization was measured, it was 0.1 g / cm 3 , which was 10 times the value in the case where no ultrasonic wave was irradiated. became. It was observed that the transmittance was improved because the orientation was adjusted. The density of the thin film was theoretically 10%.
【００１１】比較例１ 超音波を利用しなかった事及び電位掃引を１５回とした
こと以外は実施例１と同様な方法で、活性容量（３．８
×１０-3Ａ／ｃｍ2 ）を有するポリアニリン薄膜を合成
したところ、終了後の分析では、厚さとしては４０ミク
ロンであったが、一部剥離が生じていた。不透明であ
り、機械強度が乏しかった。良好な均一性及び高密度の
薄膜は得られなかった。膜の密度としては、０．０１ｇ
／ｃｍ3 であり、１％の充実率であった。Comparative Example 1 An active capacity (3.8) was obtained in the same manner as in Example 1 except that no ultrasonic wave was used and the potential sweep was performed 15 times.
When a polyaniline thin film having (× 10 −3 A / cm 2 ) was synthesized, the analysis after the completion showed that the thickness was 40 μm, but some peeling occurred. It was opaque and had poor mechanical strength. A thin film with good uniformity and high density was not obtained. The density of the film is 0.01 g
/ Cm 3, which is a 1% fulfillment rate.
【００１２】実施例２ 正逆電位掃引する代わりに一定電流密度１ｍＡ／ｃ
ｍ2 、１５分とした以外は実施例１と同様にしてポリア
ニリン薄膜を合成した。このときの電極電位は０．８５
Ｖｖｓ．ＳＣＥに保持され、不変であった。生成した膜
の活性容量と密度は実施例１と同様のものが得られた。 比較例２ 超音波を照射しなかったこと以外は実施例２と同様にし
てポリアニリン薄膜を合成した。このときの薄膜の活性
容量と密度は、実施例２の各々約１／２及び１／６であ
った。Example 2 Instead of sweeping forward and reverse potentials, a constant current density of 1 mA / c
A polyaniline thin film was synthesized in the same manner as in Example 1 except that m 2 and 15 minutes were used. The electrode potential at this time is 0.85
Vvs. Retained by SCE and unchanged. The active capacity and density of the formed film were the same as those in Example 1. Comparative Example 2 A polyaniline thin film was synthesized in the same manner as in Example 2 except that no ultrasonic wave was applied. The active capacity and density of the thin film at this time were about １ ／ and 及 び of Example 2, respectively.
【００１３】実施例３ 電解液としてＮ−メチルピロール０．０５Ｍ、電解質と
してテトラエチルアンモニム過塩素酸塩０．１Ｍを加え
たアセトニトリルを用い、０．０〜０．８５Ｖｖｓ．Ｓ
ＣＥの電位範囲としたこと以外は、実施例１と同様にし
て重合した。得られたポリ−Ｎ−メチルピロール膜は活
性容量が５．０×１０-3Ａ／ｃｍ2 、膜厚１０ミクロ
ン、密度０．１５ｇ／ｃｍ3 であった。 比較例３ 超音波を照射しなかったことおよび掃引回数を２０回と
したこと以外は、実施例３と同様にしてポリ−Ｎ−メチ
ルピロール膜薄膜を合成した。得られたポリ−Ｎ−メチ
ルピロール膜は、活性容量が４．８×１０-3Ａ／ｃ
ｍ2 、膜厚７０ミクロン、密度０．０２ｇ／ｃｍ3 であ
った。EXAMPLE 3 Acetonitrile containing 0.05 M of N-methylpyrrole as an electrolytic solution and 0.1 M of tetraethylammonium perchlorate as an electrolyte was used. S
Polymerization was carried out in the same manner as in Example 1 except that the potential range of CE was set. The obtained poly-N-methylpyrrole film had an active capacity of 5.0 × 10 −3 A / cm 2 , a film thickness of 10 μm, and a density of 0.15 g / cm 3 . Comparative Example 3 A poly-N-methylpyrrole film thin film was synthesized in the same manner as in Example 3 except that no ultrasonic wave was applied and the number of sweeps was set to 20 times. The obtained poly-N-methylpyrrole film has an active capacity of 4.8 × 10 −3 A / c.
m 2 , thickness 70 μm, density 0.02 g / cm 3 .
【００１４】[0014]
【発明の効果】本発明の電気化学処理方法により得られ
る有機高分子薄膜電極は、従来の電解重合法により得ら
れている有機高分子薄膜に比較して密度が高く、活性容
量も大きく、電池材料としては出力容量を大きくできる
ため、工業的利用価値が高い。性能が安定しており、セ
ンサーなどの検出機能の再現性が向上している。また、
本発明の有機高分子薄膜電極の製造方法は、これまでの
電解重合法について超音波を照射しながら行えばよいの
で、その簡単に行えることができ、しかも従来よりも密
度が高く、活性容量も大きい有機高分子薄膜電極を得る
ことができる。The organic polymer thin film electrode obtained by the electrochemical treatment method of the present invention has a higher density and a larger active capacity than the organic polymer thin film obtained by the conventional electrolytic polymerization method. As a material, the output capacity can be increased, so that it has high industrial use value. The performance is stable, and the reproducibility of detection functions such as sensors is improved. Also,
The method for producing an organic polymer thin film electrode of the present invention can be performed easily by irradiating ultrasonic waves with respect to the conventional electrolytic polymerization method. A large organic polymer thin film electrode can be obtained.
【図１】本発明の有機高分子薄膜電極の縦断面図を示
す。FIG. 1 is a longitudinal sectional view of an organic polymer thin film electrode of the present invention.
１ 有機高分子薄膜電極 ２ 導電性基材 ３ 有機高分子薄膜 1 Organic polymer thin film electrode 2 Conductive substrate 3 Organic polymer thin film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 尚武 愛知県名古屋市天白区久方２−２ 豊田工 業大学第２久方寮102 (72)発明者 関本 正生 神奈川県大和市福田２−33−11 (72)発明者 錦 善則 神奈川県藤沢市藤沢１−１−23−304 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naotake Sato 2-2 Kugakata, Tenpaku-ku, Nagoya-shi, Aichi 102 102 Kumagata Dormitory 2, Toyota Technological University (72) Inventor Masao Sekimoto 2-Fukuda, Yamato-shi, Kanagawa 33-11 (72) Inventor Yoshinori Nishiki 1-1-23-304 Fujisawa, Fujisawa-shi, Kanagawa
Claims (5)
電気化学的に形成した有機高分子膜を有することを特徴
とする薄膜電極。1. A thin film electrode comprising an organic polymer film electrochemically formed on a conductive substrate while being irradiated with ultrasonic waves.
子であることを特徴とする請求項１の薄膜電極。2. The thin film electrode according to claim 1, wherein said organic polymer film is an aromatic organic oxide polymer.
１ｍｍであることを特徴とする請求項１又は請求項２の
薄膜電極。3. The method according to claim 1, wherein said organic polymer film has a thickness of 0.001 to 0.001.
The thin-film electrode according to claim 1 or 2, wherein the thickness is 1 mm.
電極の製造に当たり、前記有機高分子を形成し得る有機
化合物の電解重合を超音波を照射しながら行うことによ
り導電性基材上に有機高分子膜からなる薄膜を形成する
ことを特徴とする薄膜電極の製造方法。4. In producing a thin-film electrode having a thin film composed of an organic polymer film, an organic compound capable of forming the organic polymer is subjected to electrolytic polymerization while irradiating ultrasonic waves, thereby forming an organic polymer on the conductive substrate. A method for manufacturing a thin film electrode, comprising forming a thin film made of a polymer film.
００ｋＨｚであることを特徴とする請求項４の薄膜電極
の製造方法。5. The ultrasonic wave to be irradiated has a frequency of 5 kHz to 1
5. The method according to claim 4, wherein the frequency is 00 kHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9063074A JPH10261417A (en) | 1997-03-17 | 1997-03-17 | Organic polymer thin film electrode and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9063074A JPH10261417A (en) | 1997-03-17 | 1997-03-17 | Organic polymer thin film electrode and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10261417A true JPH10261417A (en) | 1998-09-29 |
Family
ID=13218843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9063074A Pending JPH10261417A (en) | 1997-03-17 | 1997-03-17 | Organic polymer thin film electrode and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10261417A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011510141A (en) * | 2008-01-22 | 2011-03-31 | エイチ・シー・スタルク・クレビオス・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Method for producing conductive polymer |
-
1997
- 1997-03-17 JP JP9063074A patent/JPH10261417A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011510141A (en) * | 2008-01-22 | 2011-03-31 | エイチ・シー・スタルク・クレビオス・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Method for producing conductive polymer |
| JP2014159567A (en) * | 2008-01-22 | 2014-09-04 | Hc Starck Clevios Gmbh | Method for producing electroconductive polymer |
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