JPH0762065B2 - Preparation method of organic polymer film containing metal powder - Google Patents
Preparation method of organic polymer film containing metal powderInfo
- Publication number
- JPH0762065B2 JPH0762065B2 JP2436786A JP2436786A JPH0762065B2 JP H0762065 B2 JPH0762065 B2 JP H0762065B2 JP 2436786 A JP2436786 A JP 2436786A JP 2436786 A JP2436786 A JP 2436786A JP H0762065 B2 JPH0762065 B2 JP H0762065B2
- Authority
- JP
- Japan
- Prior art keywords
- organic polymer
- metal
- metal powder
- polymer film
- preparation
- 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 - Lifetime
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は有機モノマーを電解酸化重合することにより有
機高分子膜を作成する方法、特に該高分子内に金属粉末
を含有させた有機高分子膜の製造法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing an organic polymer film by electrolytically oxidatively polymerizing an organic monomer, and in particular to an organic polymer film containing a metal powder in the polymer. It relates to the manufacturing method.
従来の技術 電解酸化重合によって得られる高分子は、その合成のコ
ントロールが電圧，通電電気量によって行なう事が出来
るため、又最近では合成した高分子のもつ物性におい
て、電子伝導性あるいは半導体特性を附与させうること
から活発に検討されている。例えば、有機高分子とし
て、ポリピロールを例にとると、その電解重合は次の如
く行なわれる。即ち、電解液として、有機容媒（例え
ば、アセトニトリル，デメチルホルムアミド，プロピレ
ンカーボネート等）に、ホウフッ化リチウム（LiB
F4），過塩素酸リチウム（LiclO4）等の電解質を溶解し
た溶液中に重合したい有機モノマー（この場合、ピロー
ル）を溶解させた電解液を用い、該電解液中に試料電極
と対向電極、更に必要に応じて、試料電極に印加する電
位を規制するための参照電極を挿入し、試料電極に正電
圧を印加しながら、ピロールを電解酸化することによ
り、ピロールポリマーを試料電極表面に重合析出させて
いる。このようにして得られた有機高分子は、高分子内
への陰イオン、例えばBF4 -のドーピング又は脱ドーピン
グにより、電子伝導性の程度あるいは半導体特性を変化
させうる性質を有している。したがって、これらの特性
を利用して、電池,FETトランジスター，電磁波シールド
材への応用が検討されている。しかし、電池とした場
合、そのエネルギー密度が比較的小さい事、FETトラン
ジスターとした場合、有分子が緻密で、かつ平滑な状態
で析出させる事が困難なため、P.N接合面の接合状態が
悪く、従来のFETと比較して優れた特性が少ないなどの
ことから、その応用展開を活発に進めるための魅力に欠
けていた。2. Description of the Related Art Polymers obtained by electrolytic oxidative polymerization can be controlled by the voltage and the amount of electricity applied, and recently, the physical properties of the synthesized polymers have electronic conductivity or semiconductor characteristics. It is being actively studied because it can be given. For example, taking polypyrrole as the organic polymer, the electrolytic polymerization is carried out as follows. That is, as an electrolytic solution, an organic solvent (for example, acetonitrile, demethylformamide, propylene carbonate, etc.) and lithium borofluoride (LiB
F 4 ), lithium perchlorate (LiclO 4 ) and other electrolytes are dissolved in an organic monomer to be polymerized (in this case, pyrrole) is used as an electrolyte solution. If necessary, a reference electrode for regulating the potential applied to the sample electrode is inserted, and the pyrrole polymer is polymerized on the sample electrode surface by electrolytically oxidizing pyrrole while applying a positive voltage to the sample electrode. Have been deposited. The organic polymer thus obtained has a property that the degree of electronic conductivity or semiconductor characteristics can be changed by doping or dedoping anion, for example, BF 4 − into the polymer. Therefore, using these characteristics, application to batteries, FET transistors, and electromagnetic wave shielding materials is being studied. However, in the case of a battery, the energy density is relatively small, and in the case of a FET transistor, it is difficult to deposit the molecules with a dense and smooth state, so the bonding state of the PN junction surface is poor, It lacks the attractiveness for actively promoting the application development because it has less excellent characteristics than the conventional FET.
発明者らは、これら問題点の解消のために有機高分子内
に各種機能を有した微粉末を含有した電解有機高分子膜
を製造する方法を検討した、該方法は、金属，金属酸化
物，金属窒化物等の微粉末を電解液中に分散しながら、
あるいは微粉末を電解液で湿潤させた中で電極表面に電
解析出させるものであった。In order to solve these problems, the inventors have studied a method for producing an electrolytic organic polymer film containing fine powder having various functions in an organic polymer. The method is a metal or metal oxide. , While dispersing fine powder such as metal nitride in the electrolyte,
Alternatively, the fine powder was electrolytically deposited on the electrode surface while being moistened with the electrolytic solution.
発明が解決しようとする問題点 前記、金属微粉末を有機高分子内に含有させる方法で
は、あらゆる金属を有機高分子内に含有させることが困
難であった。なぜならば、有機高分子膜を合成するため
には、電解酸化反応を使用することから、電解酸化を受
けても程んど電解液に溶解しない金属，チタン，タンタ
ル，タングステン，モリブデン，ニオブ等の弁作用金属
しか使用出来なかった。本発明では亜鉛，インジウム，
ニッケル，鉛、銅等の一般金属を含有した有機高分子膜
を得んがためのものである。Problems to be Solved by the Invention In the above-mentioned method of incorporating the metal fine powder into the organic polymer, it has been difficult to incorporate all metals into the organic polymer. Because an electrolytic oxidation reaction is used to synthesize an organic polymer film, metals, titanium, tantalum, tungsten, molybdenum, niobium, etc., which are not substantially dissolved in an electrolytic solution even when subjected to electrolytic oxidation, are used. Only valve metal could be used. In the present invention, zinc, indium,
This is for obtaining organic polymer films containing general metals such as nickel, lead and copper.
問題点を解決するための手段 有機高分子合成のための電解液中に、含有させたい金属
を酸化物の形態で含有させ、電解重合を行ない、金属酸
化物よりなる微粉末を含有した有機高分子を作成する。
つづいて得られた有機高分子を還元すると、該高分子内
の金属酸化物は還元され、金属微粉末を含有した有機高
分子を得ることが出来る。Means for Solving Problems The metal to be contained in the electrolytic solution for organic polymer synthesis is contained in the form of an oxide, and electrolytic polymerization is carried out. Create a molecule.
Subsequently, when the obtained organic polymer is reduced, the metal oxide in the polymer is reduced, and an organic polymer containing fine metal powder can be obtained.
作 用 一般に、ほとんどの金属は電解液中で電子を引き抜かれ
ると、金属イオン（M+）となって溶出する。即ち、有機
物の電解酸化が進行する電位より卑な電位に金属の酸化
還元電位をもつ金属は、この溶解反応が起る。したがっ
て、電気的に陰性度の比較的低い金属，銅，亜鉛，イン
ジウム等では、特に有機高分子を析出（電解酸化重合）
させるための電位を印加すると、金属の溶解が起る。こ
れに反し、金属酸化物の酸化還元電位は比較的高い電位
を示すため、化学的にも電気化学的にも安定で溶解現象
が起こりにくいものとなる。したがって、有機高分子内
に含有させたい金属微粉末を化学的にも電気化学的にも
安定な状態にすることにより有機高分子と共に共析出さ
せることが可能であり、該高分子を還元することによ
り、希望する金属微粉末を含有させた有機高分子が得る
ことが可能となる。Operation In general, most metals elute as metal ions (M + ) when electrons are extracted from the electrolyte. That is, this dissolution reaction occurs with a metal having a redox potential of the metal at a potential lower than the potential at which the electrolytic oxidation of the organic substance proceeds. Therefore, in the case of metals, such as copper, zinc, and indium, which have relatively low electronegativity, organic polymers are particularly deposited (electrolytic oxidation polymerization).
Application of a potential for causing the dissolution of the metal occurs. On the contrary, since the redox potential of the metal oxide exhibits a relatively high potential, it is chemically and electrochemically stable, and the dissolution phenomenon does not easily occur. Therefore, it is possible to co-precipitate with the organic polymer by making the fine metal powder to be contained in the organic polymer stable both chemically and electrochemically, and to reduce the polymer. This makes it possible to obtain an organic polymer containing the desired fine metal powder.
実施例 以下、実施例をもとに本発明を説明する。EXAMPLES Hereinafter, the present invention will be described based on examples.
実施例１ 図は本発明の有機高分子を得るために用いた電解重合装
置を示す。図中１はアノード室，カソード室を分離する
ガラス製のセパレーター２を中間に介在させた電解槽で
ある。３は有機高分子を得るためのステンレススティー
ル（1cm2）製の試料電極であり、４は試料電極に印加す
るで電位を規制するために使用した参照電極で、ここで
は銀線を用いた。５は白金電極より対向電極、６は電解
液で0.1Mピロールを含む0.5MLiBF4/アセトニトリルを用
いた。７は金属酸化物微粉末で、ここでは酸化インジウ
ム（粒径50μ以下）粉末を用いた。８は電解液をかくは
んするためのかくはん棒で、9,10は各々、かくはん棒を
支えるための軸受と回転を伝えるためのプーリーであ
る。該電解液をかくはんしながら、ポテンシオスタット
11とファンクションゼネレーター12を用い電解電位を規
制しながら電解した。電解条件は20℃，＋0.7V（VvsA
g）で１時間電解した。つづいて試料電極に析出した高
分子を電解槽１より取り出し、1M−LiClO4/プロピレン
カーボネート電解液の入った別の電解槽中で、Ag参照電
極に対して−1.8Vの電位で１時間電解還元を行なった。
還元前の有機高分子は銀参照電極に対しCa＋0.3Vの開路
電圧を示したが、還元後はCa−1.2Vの電位を示し、イン
ジウム金属の酸化還元電位（Ca−1.3VvsAg）に近い値を
示した。比較のため、酸化インジウムを含まない高分子
を同様に還元したが、その開路電圧は安定せず、１時間
後には＋0.2V附近まで移動した。Example 1 FIG. 1 shows an electrolytic polymerization apparatus used to obtain the organic polymer of the present invention. In the figure, 1 is an electrolytic cell in which a glass separator 2 for separating the anode chamber and the cathode chamber is interposed in the middle. Reference numeral 3 is a sample electrode made of stainless steel (1 cm 2 ) for obtaining an organic polymer, and reference numeral 4 is a reference electrode used to regulate the potential when applied to the sample electrode, and a silver wire is used here. 5 is a counter electrode rather than a platinum electrode, and 6 is an electrolytic solution, which is 0.5 M LiBF 4 / acetonitrile containing 0.1 M pyrrole. 7 is a metal oxide fine powder, and here, indium oxide (particle size: 50 μm or less) powder was used. Reference numeral 8 is a stirring rod for stirring the electrolytic solution, and 9 and 10 are bearings for supporting the stirring rod and pulleys for transmitting rotation. While stirring the electrolytic solution, a potentiostat
11 and function generator 12 were used for electrolysis while regulating the electrolysis potential. Electrolysis conditions are 20 ℃, + 0.7V (VvsA
g) was electrolyzed for 1 hour. Then the polymer was precipitated on the sample electrode was taken out from the electrolytic cell 1, in a different electrolytic cell containing the 1M-LiClO 4 / propylene carbonate electrolyte, 1 hour electrolysis at -1.8V potential vs Ag reference electrode Reduction was performed.
The organic polymer before reduction showed an open circuit voltage of Ca + 0.3 V against the silver reference electrode, but after reduction it showed a potential of Ca -1.2 V, which was close to the redox potential of indium metal (Ca-1.3 V vs Ag). showed that. For comparison, a polymer containing no indium oxide was similarly reduced, but its open circuit voltage was not stable and moved to around +0.2 V after 1 hour.
実施例２ 電解液中に含有させる酸化物粉末として、酸化亜鉛（粒
径30μ以下）を用いた以外は実施例１と全く同様にし
て、亜鉛粉末を含有する有機高分子を作成した。得られ
た該高分子の開路電圧はCa−1.40V（VvsAg）を示す、含
有する粉末が亜鉛に還元されていることを認めうること
が出来た。Example 2 An organic polymer containing zinc powder was prepared in exactly the same manner as in Example 1 except that zinc oxide (particle size: 30 μm or less) was used as the oxide powder contained in the electrolytic solution. The open circuit voltage of the obtained polymer was Ca-1.40 V (VvsAg), and it could be confirmed that the powder contained therein was reduced to zinc.
以上、上記実施例では、インジウム，亜鉛粉末のみを含
有した有機高分子の作成法を例示したが、他金属、例え
ば鉛，銅，銀，スズ等、金属単独では、有機高分子の電
解酸化重合の際に溶解するため使用出来ない金属粉末を
も、本発明によって有機高分子内に含有させうるもので
ある。In the above examples, the method for producing an organic polymer containing only indium and zinc powders has been described. Metal powder that cannot be used because it dissolves during the process can be contained in the organic polymer according to the present invention.
発明の効果 本発明によれば、あらゆる金属粉末を有機高分子内に含
有させることができ、有機高分子自体の電気伝導性を向
上させることが可能となり、導電材料としての応用範囲
が拡大される。又、例えば電池電極材に応用することに
より、その電極のもつエネルギー密度の向上が計れるこ
となど、その応用効果は極めて大である。EFFECTS OF THE INVENTION According to the present invention, any metal powder can be contained in the organic polymer, the electric conductivity of the organic polymer itself can be improved, and the range of application as a conductive material is expanded. . Further, for example, when applied to a battery electrode material, the energy density of the electrode can be improved, and the application effect is extremely large.
図は、本発明の一実施例における電解装置を示す断面図
である。 ３……試料電極、４……参照電極、５……対向電極、６
……電解液、７……金属酸化物微粉末。FIG. 1 is a sectional view showing an electrolysis device according to an embodiment of the present invention. 3 ... sample electrode, 4 ... reference electrode, 5 ... counter electrode, 6
…… Electrolyte, 7 …… Metal oxide fine powder.
Claims (1)
せるよう有機高分子膜の電解合成を行い、然る後、前記
高分子を還元することを特徴とする金属粉末を含有した
有機高分子膜の作成法。1. An organic polymer containing a metal powder, characterized in that an organic polymer film is electrolytically synthesized so as to contain an oxide powder of a metal to be contained, and then the polymer is reduced. How to make a membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2436786A JPH0762065B2 (en) | 1986-02-06 | 1986-02-06 | Preparation method of organic polymer film containing metal powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2436786A JPH0762065B2 (en) | 1986-02-06 | 1986-02-06 | Preparation method of organic polymer film containing metal powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62181329A JPS62181329A (en) | 1987-08-08 |
| JPH0762065B2 true JPH0762065B2 (en) | 1995-07-05 |
Family
ID=12136219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2436786A Expired - Lifetime JPH0762065B2 (en) | 1986-02-06 | 1986-02-06 | Preparation method of organic polymer film containing metal powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0762065B2 (en) |
-
1986
- 1986-02-06 JP JP2436786A patent/JPH0762065B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62181329A (en) | 1987-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6117590A (en) | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same | |
| EP1108271B1 (en) | Paste-like masses for electrochemical components, layers produced therefrom, and electrochemical components | |
| US4717634A (en) | Electric cells utilizing polyaniline as a positive electrode active material | |
| KR100777504B1 (en) | Nano-crystalline material-containing pastes for electrochemical structural elements and layers and electrochemical structural elements prepared therefrom | |
| JP2003513429A (en) | Film for electrochemical structural member and method for producing the film | |
| EP0124702A1 (en) | Reversible electrochemical doping of conjugated polymers | |
| JPH10505705A (en) | Secondary battery using organic sulfur / metal charge conductive material for positive electrode | |
| KR850007818A (en) | How to make alloyed negative electrodes and devices using them | |
| US4695521A (en) | Conjugated polymer as substrate for the plating of alkali metal in a nonaqueous secondary battery | |
| Trinidad et al. | Electrochemical behaviour of polypyrrole films as secondary battery electrodes in LiClO4-propylene carbonate | |
| CN104272517B (en) | Indium stannum binary anode for rechargeable magnesium ion accumulator | |
| US5849045A (en) | Method for preparing and using electroconductive polymer composites as positive electrode active materials to prepare secondary batteries | |
| CN113299869A (en) | Method for inhibiting growth of zinc dendrite in zinc ion battery/capacitor | |
| Barisci et al. | Electrochemical preparation of polypyrrole colloids using a flow cell | |
| WO1993014528A1 (en) | Secondary battery | |
| JPH0762065B2 (en) | Preparation method of organic polymer film containing metal powder | |
| EP0145843A2 (en) | Electrically conductive composites comprising p-doped acetylene having conductive coatings and conjugated aromatic polymers and process therefor | |
| Choi et al. | Lithiophilic Protective Dual Layer Enabling Stable Electrodeposition of Lithium at High Current Density | |
| Stanković et al. | Some aspects of the electrochemical synthesis of polypyrrole | |
| Passerini et al. | New Thin‐Layer Solid State Lithium Polymer Batteries | |
| Maxfield et al. | Surface Modification of Polyacetylene (PA) for Electrochemical Applications | |
| CN104272516B (en) | Indium-tin binary anode for rechargeable Magnesium ion battery | |
| US4705728A (en) | Solid polymer electrolyte and production method | |
| JPH09245848A (en) | Light charging type thin power supply element | |
| JPH04179049A (en) | Battery negative electrode |