JP2713619B2 - Electrolytic polymerization apparatus for producing conductive polymer film and method for producing membrane - Google Patents
Electrolytic polymerization apparatus for producing conductive polymer film and method for producing membraneInfo
- Publication number
- JP2713619B2 JP2713619B2 JP1270328A JP27032889A JP2713619B2 JP 2713619 B2 JP2713619 B2 JP 2713619B2 JP 1270328 A JP1270328 A JP 1270328A JP 27032889 A JP27032889 A JP 27032889A JP 2713619 B2 JP2713619 B2 JP 2713619B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- producing
- voltage
- polymer film
- potential
- 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.)
- Expired - Fee Related
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は導電性高分子膜製造用電解重合装置に関し、
更に詳しくは直流電圧と交流電圧を利用して複数の基板
上に、同時に、しかも均一な導電性高分子膜を電解重合
によって製造する装置及び該装置を使用した導電性高分
子膜の製造方法に関する。The present invention relates to an electrolytic polymerization apparatus for producing a conductive polymer film,
More specifically, the present invention relates to an apparatus for manufacturing a conductive polymer film simultaneously and uniformly on a plurality of substrates by using a DC voltage and an AC voltage by electrolytic polymerization, and a method for manufacturing a conductive polymer film using the apparatus. .
導電性高分子膜の製造法としての電解法を例にとる
と、その電解重合法には定電流法、定電圧法、定電位
法、電位走査法等がある。しかし、膜の種類によっては
電解条件に制約のある場合が多い。例えば、アニリンの
電解重合に際しては上記のいずれの方法でも製造するこ
とができるが、その主流は定電位法と電位走査法であ
り、１対の電極を電解液中に挿入してアニリンを重合す
ると、定電位法ではパウダー状の、電位走査法ではフィ
ルム状のポリアニリンが得られる。Taking an electrolytic method as an example of a method for producing a conductive polymer film, the electrolytic polymerization method includes a constant current method, a constant voltage method, a constant potential method, a potential scanning method, and the like. However, electrolysis conditions are often restricted depending on the type of film. For example, in the case of electrolytic polymerization of aniline, any of the above methods can be used, but the mainstream is a constant potential method and a potential scanning method, and when aniline is polymerized by inserting a pair of electrodes into an electrolytic solution. A powdery polyaniline can be obtained by the constant potential method, and a film-like polyaniline can be obtained by the potential scanning method.
このポリアニリンを正極として、負極にリチウムを用
いた二次電池として作動させた場合の電池性能では電位
走査法で製造したポリアニリンの方が上回っている。The battery performance when operated as a secondary battery using this polyaniline as a positive electrode and lithium as a negative electrode is higher than that of the polyaniline produced by the potential scanning method.
第２図はこの電位走査法によるポリアニリンの重合装
置の１例を示したものである。第２図において、重合槽
１の中に電解液（過塩素酸＋アニリン＋水）２を入れ、
基板（チタン）３（＋極）の一部を白金メッキした部分
（ポリアニリンを合成しようとする極面）４と対極（Ti
-Ptメッキ）５とポリアニリンを合成しようとする極面
４に参照電極６の先端を近付けて配置した三極に、ポテ
ンシオスタット７の端子と作用電極３用のリード線８、
対極５用のリード線9,参照電極６用のリード線10が接続
されている。関数発生器11は電位の走査速度と電位の走
査範囲を制御するための装置である。FIG. 2 shows an example of a polyaniline polymerization apparatus using this potential scanning method. In FIG. 2, an electrolytic solution (perchloric acid + aniline + water) 2 is put into a polymerization tank 1,
A part of the substrate (titanium) 3 (+ electrode) is plated with platinum (the surface on which polyaniline is to be synthesized) 4 and a counter electrode (Ti
The terminal of the potentiostat 7 and the lead wire 8 for the working electrode 3 are disposed on the three poles in which the tip of the reference electrode 6 is arranged close to the pole face 4 where the polyaniline is to be synthesized.
A lead wire 9 for the counter electrode 5 and a lead wire 10 for the reference electrode 6 are connected. The function generator 11 is a device for controlling a potential scanning speed and a potential scanning range.
この装置でポリアニリンを合成する場合、作用電極面
４の自然電位の状態から任意の走査電圧信号が関数発生
器11よりポテンシオスタット７に送られる。ポテンシオ
スタット７は作用電極面４と参照電極６の間の電位が関
数発生器11より入ってきた電圧信号に応じた電位になる
よう電流を流す。一般的に、自然電位から徐々に貴な電
位へ走査し、作用電極４を酸化状態にして特定の電位ま
で上昇させた後、今度は逆に、電位を卑な方向へ走査す
る。この走査を何千回、何万回と行うことにより、走査
回数に応じたポリアニリンが得られる。When synthesizing polyaniline with this device, an arbitrary scanning voltage signal is sent from the function generator 11 to the potentiostat 7 from the state of the natural potential of the working electrode surface 4. The potentiostat 7 supplies a current so that the potential between the working electrode surface 4 and the reference electrode 6 becomes a potential corresponding to the voltage signal input from the function generator 11. In general, scanning is performed gradually from a natural potential to a noble potential, the working electrode 4 is oxidized to a specific potential, and then the potential is scanned in a negative direction. By performing this scanning several thousand times and tens of thousands of times, polyaniline corresponding to the number of times of scanning can be obtained.
さらに、定電位重合法の場合には第２図の関数発生器
11を除いた装置で重合でき、作用電極面４の部分を一定
の電位（酸化状態）に任意の時間保持するだけで作用電
極面４上にパウダー状のポリアニリンが得られる。Further, in the case of the constant potential polymerization method, the function generator shown in FIG.
Polymerization can be carried out by using an apparatus except 11, and a powdery polyaniline can be obtained on the working electrode surface 4 simply by keeping the portion of the working electrode surface 4 at a constant potential (oxidized state) for an arbitrary time.
しかし、前述のような方法には次に示すような問題点
を有していた。However, the above-described method has the following problems.
（１）両者共、電位情報を得るための参照電極を必要と
する。(1) Both require a reference electrode for obtaining potential information.
（２）１つの装置（第２図）で１つの膜しかできないた
め、工業的には非常に生産性が悪い。従って大量に作ろ
うとすれば、（イ）大きなスペースが要る。（ロ）設備
費がかかる。等の問題点があった。(2) Since only one film can be formed by one device (FIG. 2), the productivity is extremely low industrially. Therefore, large-scale production requires (a) a large space. (B) Equipment costs are required. And so on.
さらに定電流法，定電圧法等は電位に制約を受けるポ
リアニリンの重合には、どちらかと言えば不適当であ
り、性能のよい膜を作るには電位走査法がよいが、前記
（１），（２）のような問題点を有しているため生産効
率の低さは避けられない。Furthermore, the constant current method, the constant voltage method, and the like are rather unsuitable for the polymerization of polyaniline, which is restricted by the potential, and the potential scanning method is preferable for producing a film with good performance. Due to the problem (2), low production efficiency cannot be avoided.
本発明は上記技術水準に鑑み、従来技術における問題
点を解消し、多数の基板上に同時に、しかも均一な膜を
重合生成させることができる導電性高分子膜製造用電解
重合装置及びそれを使用した導電性高分子膜の製造方法
を提供しようとするものである。In view of the above technical level, the present invention solves the problems in the prior art, and uses an electropolymerization apparatus for producing a conductive polymer film capable of polymerizing and forming a uniform film on many substrates simultaneously and using the same. It is an object of the present invention to provide a method for producing a conductive polymer film as described above.
本発明は多数の隔壁によって区分された区画に、各々
一対の電極を配置し、印加電圧可変型直流電圧と周波数
・印加電圧可変型交流電圧を同時に、電極の極性が反転
するように印加できる電源を前記電極に直列に配線して
なることを特徴とする導電性高分子膜製造用電解重合装
置及び該導電性高分子膜製造用電解重合装置を使用し、
該装置の各区画内に導電性高分子のモノマーを含む電解
液を入れ、各区画内の電極に直流電圧と交流電圧とを同
時に、かつ直列に印加することにより、各々の電極上に
導電性高分子膜を形成させることを特徴とする導電性高
分子膜の製造方法である。The present invention provides a power supply that can arrange a pair of electrodes in sections divided by a large number of partition walls, and can apply an applied voltage variable DC voltage and a frequency / applied variable AC voltage simultaneously so that the polarity of the electrodes is inverted. Using an electropolymerization apparatus for producing a conductive polymer film and an electropolymerization apparatus for producing a conductive polymer film, characterized by being wired in series with the electrodes,
An electrolytic solution containing a monomer of a conductive polymer is put in each section of the device, and a DC voltage and an AC voltage are simultaneously and serially applied to the electrodes in each section, so that the conductive A method for producing a conductive polymer film, comprising forming a polymer film.
以下、本発明の実施例を第１図によって説明する。 Hereinafter, an embodiment of the present invention will be described with reference to FIG.
前記第２図で説明したように、基板１〜12に白金メッ
キを施した部分13〜24が互いに向かい合うように配置さ
せる。各組の槽は迷走電流を防止するため、仕切り板25
〜29で電解液30〜35が他の槽の電解液と混じり合わない
ようにしている。さらに隣りの槽の近くにある電極とを
通電用リード線36〜40で接続し、両端の電極1,12は通電
用リード線41,42を介して、通信用リード線43で周波数
可変型の交流電圧印加装置44と接続されているポテンシ
オスタット45と接続した。As described with reference to FIG. 2, the parts 13 to 24 on which the platinum plating is applied to the substrates 1 to 12 are arranged so as to face each other. Each set of tanks has a partition plate 25 to prevent stray currents.
29 to 29 prevent the electrolytes 30 to 35 from being mixed with the electrolytes in other tanks. Further, the electrodes near the adjacent tank are connected by conducting leads 36 to 40, and the electrodes 1 and 12 at both ends are passed through conducting leads 41 and 42, and the communication lead 43 is used to change the frequency of the frequency variable type. It was connected to a potentiostat 45 connected to an AC voltage applying device 44.
ここで、ポテンシオスタット45と交流電圧印加装置44
はNF回路（株）からセットで発売されている通常FRAと
呼ばれているものを使用したが、直流の印加電圧と周波
数を変化させられる交流の電圧双方を重たんした電圧を
印加させられる装置であればどのようなものでもよい。Here, the potentiostat 45 and the AC voltage applying device 44
Used a device called normal FRA released as a set from NF Circuit Co., Ltd., but a device that can apply both a DC applied voltage and an AC voltage that can change the frequency Anything can be used.
試験条件を次に示す。 The test conditions are shown below.
（イ）基板・・・チタン（3cm×10cm×厚み1mm） （ロ）白金・・・電気メッキ（3cm×3cm×厚み１μ） （ハ）極板の間隔・・・1cm （ニ）電解液・・・過塩素酸（0.2M）＋アニリン（0.1
M）＋水（１） （ホ）直流印加電圧・・・＋1.2V （ヘ）交流印加電圧・・・＋6V （ト）周波数・・・50mHz （チ）電圧印加時間・・・40時間 この重合によって得られた各ポリアニリン膜１〜12の
充放電特性を調べたところ次に示す値が得られた。(A) Substrate: Titanium (3cm x 10cm x 1mm thick) (b) Platinum: Electroplating (3cm x 3cm x 1μ thickness) (c) Electrode spacing: 1cm (d) Electrolyte ..Perchloric acid (0.2M) + aniline (0.1
(M) + water (1) (e) DC applied voltage ... + 1.2V (f) AC applied voltage ... + 6V (g) Frequency ... 50mHz (h) Voltage application time ... 40 hours This polymerization When the charge / discharge characteristics of each of the polyaniline films 1 to 12 obtained as described above were examined, the following values were obtained.
（１）クローン効果・・・多少のばらつきはあるが、全
て93％以上のものが得られた。(1) Cloning effect: Although there are some variations, all of them were 93% or more.
（２）エネルギー密度・・・膜重量をベースにして300
〜350W・Hr/kgとなった。（負極はリチウム） （３）出力密度・・・４〜6KW/kg（負極はリチウム） （４）サイクル寿命・・・各膜とも100サイクルの充放
電を行ったが、クーロン効率，容量の低下はみられなか
った。(2) Energy density: 300 based on film weight
~ 350W · Hr / kg. (Negative electrode is lithium) (3) Power density: 4-6KW / kg (Negative electrode is lithium) (4) Cycle life: 100 cycles of charge / discharge were performed for each film, but the coulomb efficiency and capacity decreased. Was not seen.
以上のように、初期特性としては電位走査法で重合し
た膜と同等の性能を有する膜の重合が可能で、しかも12
枚が同時に得られた。As described above, it is possible to polymerize a film having the same initial performance as that of a film polymerized by the potential scanning method.
Sheets were obtained at the same time.
上記の実施例では、１度に12枚しか重合できなかった
が、ポテンシオスタットあるいは周波数と印加電圧を変
えられる交流電圧と、さらに印加電圧を変えられる直流
電圧の双方を同時に印加できる電源装置で、電圧，電流
の容量の大きいものを使用すれば、何枚でも同時に重合
させることができる。In the above embodiment, only 12 sheets could be polymerized at one time, but a potentiostat or a power supply device capable of simultaneously applying both an AC voltage capable of changing the frequency and the applied voltage and a DC voltage capable of further changing the applied voltage are used. If a large voltage and current capacity is used, any number of sheets can be polymerized simultaneously.
以上の実施例では、ポリアニリンの製造について説明
したが、これ以外にポリピロール、ポリチオフェン、ポ
リメチルチオフェンなどの導電性高分子膜の製造にも本
発明装置が適用されることは云うまでもない。Although the production of polyaniline has been described in the above embodiments, it goes without saying that the apparatus of the present invention is also applicable to the production of conductive polymer films such as polypyrrole, polythiophene, and polymethylthiophene.
本発明によれば、参照電極なしに、しかも１つの電源
装置により大量の導電性高分子膜を製造できる装置及び
それを使用した導電性高分子膜の製造方法が提供され
る。ADVANTAGE OF THE INVENTION According to this invention, the apparatus which can manufacture a large amount of conductive polymer films with one power supply device without a reference electrode, and the manufacturing method of the conductive polymer film using the same are provided.
第１図は本発明の一実施例装置の概略図、第２図は従来
の電位走査法による電解重合装置の概略図である。FIG. 1 is a schematic view of an apparatus according to one embodiment of the present invention, and FIG. 2 is a schematic view of a conventional electrolytic polymerization apparatus using a potential scanning method.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−30689（ＪＰ，Ａ) 特開 昭63−99797（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-30689 (JP, A) JP-A-63-99797 (JP, A)
Claims (2)
々一対の電極を配置し、印加電圧可変型直流電圧と周波
数・印加電圧可変型交流電圧を同時に、電極の極性が反
転するように印加できる電源を前記電極に直列に配線し
てなることを特徴とする導電性高分子膜製造用電解重合
装置。1. A pair of electrodes are arranged in sections divided by a number of partition walls, and a variable applied voltage DC voltage and a variable frequency / applied voltage AC voltage are simultaneously applied so that the polarity of the electrodes is reversed. An electrolytic polymerization apparatus for producing a conductive polymer film, wherein a power source capable of being provided is wired in series with the electrode.
解重合装置を使用し、該装置の各区画内に導電性高分子
のモノマーを含む電解液を入れ、各区画内の電極に直流
電圧と交流電圧とを同時に、かつ直列に印加することに
より、各々の電極上に導電性高分子膜を形成させること
を特徴とする導電性高分子膜の製造方法。2. An electrolytic polymerization apparatus for producing a conductive polymer film according to claim 1, wherein an electrolytic solution containing a monomer of a conductive polymer is put in each section of the apparatus, and an electrode in each section is provided. A method for producing a conductive polymer film, comprising applying a DC voltage and an AC voltage simultaneously and in series to form a conductive polymer film on each electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270328A JP2713619B2 (en) | 1989-10-19 | 1989-10-19 | Electrolytic polymerization apparatus for producing conductive polymer film and method for producing membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1270328A JP2713619B2 (en) | 1989-10-19 | 1989-10-19 | Electrolytic polymerization apparatus for producing conductive polymer film and method for producing membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03134191A JPH03134191A (en) | 1991-06-07 |
| JP2713619B2 true JP2713619B2 (en) | 1998-02-16 |
Family
ID=17484735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1270328A Expired - Fee Related JP2713619B2 (en) | 1989-10-19 | 1989-10-19 | Electrolytic polymerization apparatus for producing conductive polymer film and method for producing membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2713619B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057103A (en) * | 2011-09-08 | 2013-03-28 | Tokyo Institute Of Technology | Method for manufacturing polymer film, conductive substrate with polymer film, and electropolymerization apparatus for manufacturing polymer film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6947970B2 (en) * | 2017-07-14 | 2021-10-13 | 富士通株式会社 | Photoelectrochemical reactor and control method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130689A (en) * | 1984-07-23 | 1986-02-12 | Matsushita Electric Ind Co Ltd | Electrolytically polymerizing method |
| JPS6399797A (en) * | 1986-10-16 | 1988-05-02 | Toshiba Corp | Variable voltage and variable frequency power source |
-
1989
- 1989-10-19 JP JP1270328A patent/JP2713619B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057103A (en) * | 2011-09-08 | 2013-03-28 | Tokyo Institute Of Technology | Method for manufacturing polymer film, conductive substrate with polymer film, and electropolymerization apparatus for manufacturing polymer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03134191A (en) | 1991-06-07 |
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