JP3453200B2 - Method for producing surface-modified conductive polymer compound film - Google Patents
Method for producing surface-modified conductive polymer compound filmInfo
- Publication number
- JP3453200B2 JP3453200B2 JP26248994A JP26248994A JP3453200B2 JP 3453200 B2 JP3453200 B2 JP 3453200B2 JP 26248994 A JP26248994 A JP 26248994A JP 26248994 A JP26248994 A JP 26248994A JP 3453200 B2 JP3453200 B2 JP 3453200B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- plasma
- graft polymerization
- conductive polymer
- methylthiophene
- 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
Links
- 229920001940 conductive polymer Polymers 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 50
- 229920000767 polyaniline Polymers 0.000 description 39
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910020366 ClO 4 Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- MYCQSOCJLZBPAT-UHFFFAOYSA-N 2-methylprop-2-enoic acid;potassium Chemical compound [K].CC(=C)C(O)=O MYCQSOCJLZBPAT-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面改質した導電性高分
子化合物からなる膜（以下、導電性高分子化合物からな
る膜を単に「導電性高分子化合物」という）の製造方法
に関する。本発明の製造方法により得られる導電性高分
子化合物は、高エネルギー密度の高分子バッテリー用電
極、光電池、電子素子、半導体素子等の電極として好適
に利用できる。BACKGROUND OF THE INVENTION The present invention relates to a film made of a surface-modified conductive polymer compound (hereinafter referred to as a conductive polymer compound).
Film is simply referred to as "conductive polymer compound") . The conductive polymer compound obtained by the production method of the present invention can be suitably used as an electrode for a polymer battery having a high energy density, a photoelectric cell, an electronic element, a semiconductor element, or the like.
【０００２】[0002]
【従来の技術】従来、導電性化合物表面にイオン交換基
を形成させ、カチオンのみを通過させる方法としては、
イオン交換基を有する高分子を溶媒に溶解させ、直接導
電性高分子表面に塗布し、乾燥させてイオン交換膜を形
成する方法が行われていた。2. Description of the Related Art Conventionally, as a method for forming an ion-exchange group on the surface of a conductive compound and allowing only cations to pass,
A method has been used in which a polymer having an ion exchange group is dissolved in a solvent, directly coated on the surface of a conductive polymer, and dried to form an ion exchange membrane.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの従来
技術による導電性高分子化合物膜の表面にイオン交換膜
を塗布する方法は、導電性高分子膜表面が平滑でないと
イオン交換膜の厚さが不均一となり、厚さも数百μｍ以
上であり、イオン透過の抵抗値が大きくなること、ま
た、ピンホール等の欠陥ができやすいという問題があ
り、これらの点について早急な解決が望まれていた。本
発明は上記従来技術の問題点を解消し、均一な膜厚で選
択的に且つ容易にイオンを透過させる表面改質高分子化
合物膜の製造方法を提供することを目的とする。However, the method of applying an ion exchange membrane to the surface of a conductive polymer compound membrane according to these prior arts is such that if the surface of the conductive polymer membrane is not smooth, the thickness of the ion exchange membrane is large. Is non-uniform, the thickness is several hundreds of μm or more, the resistance value of ion permeation is large, and defects such as pinholes are likely to occur, and urgent solution to these points is desired. It was The present invention is to solve the above prior art, and an object that you provide a method for producing selectively and easily surface-modifying polymer membranes that transmits ions with a uniform thickness.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決する手段
として、本発明は導電性高分子からなる膜の表面にイオ
ン交換基を有する高分子を不活性ガス雰囲気下でプラズ
マ照射しグラフト重合させることを特徴とする。また、
本発明は液相法または／及び気相法により上記グラフト
重合をさせることを特徴とする。 Means for Solving the Problems As a means for solving the above problems , the present invention is directed to graft polymerization by conducting plasma irradiation of a polymer having an ion exchange group on the surface of a film made of a conductive polymer in an inert gas atmosphere. it characterized thereby. Also,
The present invention uses the liquid phase method and / or the gas phase method to perform the above grafting.
It is characterized in that it is polymerized.
【０００５】[0005]
【作用】本発明者らは導電性高分子化合物からなる電極
の性能向上を狙って導電性高分子化合物表面に対してプ
ラズマを用いて改質することに成功した。このような例
は従来知られていない。本発明で得られる表面改質され
た導電性高分子は、イオン交換膜を塗布した導電性高分
子と同じ働きを有し、しかもイオン交換膜として働く導
電性高分子表面のグラフト鎖は厚さ数μｍ以下と極めて
薄く、イオン透過の抵抗が小さいこと、また、ピンホー
ル等の欠陥の問題がないという優れた点を有する。The present inventors have succeeded in modifying the surface of the conductive polymer compound with plasma in order to improve the performance of the electrode made of the conductive polymer compound. Such an example has not hitherto been known. The surface-modified conductive polymer obtained in the present invention has the same function as the conductive polymer coated with the ion exchange membrane, and the graft chain on the surface of the conductive polymer that functions as the ion exchange membrane is thick. It is extremely thin with a thickness of several μm or less, has a low resistance to ion permeation, and has the advantage that there is no problem of defects such as pinholes.
【０００６】[0006]
ポリアニリン膜表面へのビニルスルホン酸の液相法プラ
ズマグラフト重合：
（１）ポリアニリン膜の調製：電解液としてアニリン
１．０ｍｏｌ／リットル及び過塩素酸２ｍｏｌ／リット
ルの水溶液、作用極にステンレスプレート、対極に白
金、参照電極にＡｇ／ＡｇＣｌを用い、重合温度２０
℃、電解電流密度５ｍＡ／ｃｍ2 、電解重合時間５分間
として、ポリアニリン電解重合物を調製した。重合後、
ポリアニリン膜をイオン交換水で洗浄し、２０℃で真空
乾燥した。Liquid Phase Plasma Graft Polymerization of Vinyl Sulfonic Acid on Polyaniline Membrane: (1) Preparation of Polyaniline Membrane: Aqueous solution of aniline 1.0 mol / liter and perchloric acid 2 mol / liter as electrolyte, stainless steel plate as the working electrode, counter electrode Platinum as the reference electrode and Ag / AgCl as the reference electrode at a polymerization temperature of 20
A polyaniline electrolytic polymer was prepared at a temperature of 5 ° C., an electrolytic current density of 5 mA / cm 2 , and an electrolytic polymerization time of 5 minutes. After polymerization,
The polyaniline membrane was washed with ion-exchanged water and vacuum dried at 20 ° C.
【０００７】（２）プラズマグラフト重合：プラズマグ
ラフト重合のモノマー溶液は、２．６ｍｏｌ／リットル
のビニルスルホン酸水溶液である。ポリアニリン膜をア
ルゴン雰囲気０．１５Ｔｏｒｒで１００Ｗ、１分間プラ
ズマ照射した後、２．６ｍｏｌ／リットルのビニルスル
ホン酸水溶液中に４８時間浸漬し、グラフト重合させ
た。重合後、ポリアニリン膜をイオン交換水で洗浄し、
２０℃で真空乾燥した。Ｘ線光電子スペクトルによれ
ば、プラズマグラフト重合処理前に認められなかった２
６５ｅＶのＳ2Pのピークがプラズマグラフト重合後に認
められた。赤外線吸収スペクトルによれば、プラズマグ
ラフト重合後、１，１８０ｃｍ-1及び１，０７０ｃｍ-1
にＳ＝Ｏの伸縮振動の吸収が認められた。また、走査電
子顕微鏡観察によれば、プラズマグラフト重合において
ポリアニリン膜のフィブリル構造の上にグラフト層の形
成が認められた。これらの結果より、ポリアニリン膜表
面にビニルスルホン酸がグラフト重合したといえる。(2) Plasma graft polymerization: The monomer solution for plasma graft polymerization is a 2.6 mol / liter aqueous solution of vinyl sulfonic acid. The polyaniline film was plasma-irradiated in an argon atmosphere of 0.15 Torr for 100 W for 1 minute, and then immersed in a 2.6 mol / liter aqueous solution of vinyl sulfonic acid for 48 hours for graft polymerization. After polymerization, the polyaniline membrane is washed with ion-exchanged water,
It was vacuum dried at 20 ° C. According to the X-ray photoelectron spectrum, it was not observed before the plasma graft polymerization treatment.
Peak of S 2P of 65eV was observed after the plasma graft polymerization. According to infrared absorption spectrum, after the plasma graft polymerization, 1,180Cm -1 and 1,070Cm -1
Absorption of stretching vibration of S = O was observed. Further, scanning electron microscope observation confirmed formation of a graft layer on the fibril structure of the polyaniline film in plasma graft polymerization. From these results, it can be said that vinylsulfonic acid was graft-polymerized on the surface of the polyaniline film.
【０００８】〔実施例２〕
ポリアニリン膜表面へのメタクリル酸の液相法プラズマ
グラフト重合：
（１）ポリアニリン膜は実施例１と同様にして調製し
た。
（２）プラズマグラフト重合用のモノマー溶液は３．０
ｍｏｌ／リットルのメタクリル酸カリウム水溶液であ
る。ポリアニリン膜をアルゴン雰囲気０．１５Ｔｏｒｒ
で１００Ｗ、１分間プラズマ照射した後、３．０ｍｏｌ
／リットルのメタクリル酸カリウム水溶液中に４８時間
浸漬し、グラフト重合させた。重合後、ポリアニリン膜
をイオン交換水で洗浄し、２０℃で真空乾燥した。Ｘ線
光電子スペクトルによれば、プラズマグラフト重合処理
前にはＣ1Sのピークは２８５ｅＶのみに認められるが、
プラズマグラフト重合後には２８９ｅＶにもＣ 1Sのピー
クが認められた。赤外線吸収スペクトルによれば、プラ
ズマグラフト重合後、１，２１０ｃｍ-1にＣ−Ｏ伸縮振
動の吸収が認められた。また、走査電子顕微鏡観察によ
れば、プラズマグラフト重合においてポリアニリン膜の
フィブリル構造の上にグラフト層の形成が認められた。
これらの結果より、ポリアニリン膜表面にメタクリル酸
がグラフト重合したといえる。[Embodiment 2]
Liquid phase plasma of methacrylic acid on the surface of polyaniline film
Graft polymerization:
(1) Polyaniline film was prepared in the same manner as in Example 1.
It was
(2) 3.0 for the monomer solution for plasma graft polymerization
mol / l potassium methacrylate aqueous solution
It Argon atmosphere of polyaniline film 0.15 Torr
After irradiating with plasma for 100 W for 1 minute, 3.0 mol
/ L potassium methacrylic acid aqueous solution for 48 hours
It was dipped and graft polymerized. After polymerization, polyaniline film
Was washed with ion-exchanged water and vacuum dried at 20 ° C. X-ray
According to photoelectron spectrum, plasma graft polymerization treatment
C before1SPeak is observed only at 285 eV,
C after 289 eV after plasma graft polymerization 1SThe pea
Ku was recognized. According to the infrared absorption spectrum,
After Zuma graft polymerization, 1,210 cm-1C-O stretching vibration
Absorption of movement was observed. Also, by scanning electron microscope observation
Then, in plasma graft polymerization of polyaniline film
The formation of a graft layer was observed on the fibril structure.
From these results, methacrylic acid was formed on the polyaniline film surface.
Can be said to have undergone graft polymerization.
【０００９】〔実施例３〕
ポリアニリン膜表面へのビニルスルホン酸の気相法プラ
ズマグラフト重合：
（１）ポリアニリン膜は実施例１と同様にして調製し
た。
（２）気相法プラズマグラフト重合：ポリアニリン膜を
アルゴン雰囲気０．１５Ｔｏｒｒで１００Ｗ、１分間プ
ラズマ照射した後、１．０Ｔｏｒｒのビニルスルホン酸
雰囲気中に静置して、グラフト重合させた。重合後、２
０℃で真空乾燥した。Ｘ線光電子スペクトルによれば、
グラフト重合前に認められなかった２６５ｅＶのＳ2Pの
ピークがグラフト重合後に認められた。赤外線吸収スペ
クトルによれば、グラフト重合後、１，１８９ｃｍ-1及
び１，０７０ｃｍ-1にＳ＝Ｏの伸縮振動の吸収が認めら
れた。また、走査電子顕微鏡によれば、グラフト重合に
おいてポリアニリン膜のフィブリル構造の上にグラフト
層の形成が認められた。これらの結果より、プラズマ処
理することによりポリアニリン膜表面にビニルスルホン
酸がグラフト重合したといえる。Example 3 Gas Phase Plasma Graft Polymerization of Vinyl Sulfonic Acid on Polyaniline Film Surface: (1) A polyaniline film was prepared in the same manner as in Example 1. (2) Gas-phase method plasma graft polymerization: The polyaniline film was irradiated with plasma in an argon atmosphere of 0.15 Torr for 100 W for 1 minute, and then allowed to stand in a vinyl sulfonic acid atmosphere of 1.0 Torr for graft polymerization. After polymerization, 2
It was vacuum dried at 0 ° C. According to the X-ray photoelectron spectrum,
The S 2 P peak at 265 eV, which was not observed before the graft polymerization, was observed after the graft polymerization. According to infrared absorption spectrum, after graft polymerization, absorption of stretching vibration of S = O in 1,189Cm -1 and 1,070Cm -1 were observed. Moreover, according to a scanning electron microscope, formation of a graft layer was observed on the fibril structure of the polyaniline film in the graft polymerization. From these results, it can be said that vinylsulfonic acid was graft-polymerized on the surface of the polyaniline film by the plasma treatment.
【００１０】〔実施例４〕
ポリ（３−メチルチオフェン）膜表面へのビニルスルホ
ン酸の液相法プラズマグラフト重合：
（１）ポリ（３−メチルチオフェン）膜の調製：電解液
として３−メチルチオフェン０．２ｍｏｌ／リットル及
びテトラエチルアンモニウムパークロレート０．０３ｍ
ｏｌ／リットルのニトロベンゼン溶液、作用極にステン
レスプレート、対極に白金、参照電極にＡｇ／ＡｇＣｌ
を用い、重合温度２０℃、電解電流密度５ｍＡ／ｃ
ｍ2 、電解重合時間３分間として、ポリ（３−メチルチ
オフェン）電解重合物を調製した。重合後、ポリ（３−
メチルチオフェン）膜をイオン交換水で洗浄し、２０℃
で真空乾燥した。Example 4 Liquid Phase Plasma Graft Polymerization of Vinyl Sulfonic Acid on Poly (3-methylthiophene) Membrane Surface: (1) Preparation of Poly (3-methylthiophene) Membrane: 3-Methyl as Electrolyte Thiophene 0.2 mol / liter and tetraethylammonium perchlorate 0.03 m
ol / liter nitrobenzene solution, stainless steel plate for working electrode, platinum for counter electrode, Ag / AgCl for reference electrode
Polymerization temperature 20 ° C, electrolytic current density 5 mA / c
A poly (3-methylthiophene) electropolymer was prepared with m 2 and electropolymerization time of 3 minutes. After polymerization, poly (3-
Methylthiophene) membrane is washed with ion-exchanged water, 20 ° C
It was dried in vacuum.
【００１１】（２）プラズマグラフト重合：プラズマグ
ラフト重合のモノマー溶液は、２．６ｍｏｌ／リットル
のビニルスルホン酸水溶液である。ポリ（３−メチルチ
オフェン）膜をアルゴン雰囲気０．１５Ｔｏｒｒで１０
０Ｗ、１分間プラズマ照射した後、２．６ｍｏｌ／リッ
トルビニルスルホン酸水溶液中に４８時間浸漬し、グラ
フト重合させた。重合後、ポリ（３−メチルチオフェ
ン）膜をイオン交換水で洗浄し、２０℃で真空乾燥し
た。Ｘ線光電子スペクトルによれば、プラズマ処理前に
認められなかった２６５ｅＶのＳ2Pのピークがグラフト
重合後に認められた。赤外線吸収スペクトルによれば、
プラズマグラフト重合後、１，１８０ｃｍ-1及び１，０
７０ｃｍ-1にＳ＝Ｏの伸縮振動の吸収が認められた。ま
た、走査電子顕微鏡観察によれば、プラズマ処理後のグ
ラフト重合においてポリ（３−メチルチオフェン）膜の
フィブリル構造の上にグラフト層の形成が認められた。
これらの結果より、ポリ（３−メチルチオフェン）膜表
面にビニルスルホン酸がグラフト重合したといえる。(2) Plasma graft polymerization: The monomer solution for plasma graft polymerization is a 2.6 mol / liter aqueous solution of vinyl sulfonic acid. The poly (3-methylthiophene) film was subjected to argon atmosphere at 0.15 Torr for 10
After irradiating with plasma for 0 W for 1 minute, it was immersed in a 2.6 mol / liter vinyl sulfonic acid aqueous solution for 48 hours for graft polymerization. After the polymerization, the poly (3-methylthiophene) membrane was washed with ion-exchanged water and vacuum dried at 20 ° C. According to the X-ray photoelectron spectrum, an S 2 P peak of 265 eV which was not observed before the plasma treatment was observed after the graft polymerization. According to the infrared absorption spectrum,
After plasma graft polymerization, 1,180 cm -1 and 1,0
Absorption of the stretching vibration of S = O was recognized at 70 cm -1 . Further, by scanning electron microscope observation, formation of a graft layer was observed on the fibril structure of the poly (3-methylthiophene) film in the graft polymerization after the plasma treatment.
From these results, it can be said that vinyl sulfonic acid was graft-polymerized on the surface of the poly (3-methylthiophene) film.
【００１２】〔実施例５〕
ポリ（３−メチルチオフェン）膜表面へのビニルスルホ
ン酸の気相法プラズマグラフト重合：
（１）ポリ（３−メチルチオフェン）膜は実施例４と同
様にして調製した。
（２）気相法プラズマグラフト重合：ポリ（３−メチル
チオフェン）膜をアルゴン雰囲気０．１５Ｔｏｒｒで１
００Ｗ、１分間プラズマ照射した後、１．０Ｔｏｒｒの
ビニルスルホン酸雰囲気中に静置して、グラフト重合さ
せた。重合後、２０℃で真空乾燥した。Ｘ線光電子スペ
クトルによれば、プラズマ処理前に認められなかった２
６５ｅＶのＳ2Pのピークがプラズマ処理後のグラフト重
合後に認められた。赤外線吸収スペクトルによれば、プ
ラズマグラフト重合後、１，１８０ｃｍ-1及び１，０７
０ｃｍ-1にＳ＝Ｏの伸縮振動の吸収が認められた。ま
た、走査電子顕微鏡観察によれば、プラズマグラフト重
合においてポリ（３−メチルチオフェン）膜のフィブリ
ル構造の上にグラフト層の形成が認められた。これらの
結果より、ポリ（３−メチルチオフェン）膜表面にビニ
ルスルホン酸がグラフト重合したといえる。Example 5 Gas Phase Plasma Graft Polymerization of Vinyl Sulfonic Acid on Poly (3-methylthiophene) Membrane Surface: (1) Poly (3-methylthiophene) Membrane was Prepared in the Same manner as in Example 4 did. (2) Gas-phase method plasma graft polymerization: Poly (3-methylthiophene) film at 1 in an argon atmosphere of 0.15 Torr
After irradiating the plasma with 00 W for 1 minute, it was left to stand in a vinyl sulfonic acid atmosphere of 1.0 Torr to perform graft polymerization. After the polymerization, it was vacuum dried at 20 ° C. According to the X-ray photoelectron spectrum, it was not observed before plasma treatment. 2
A peak of S 2 P of 65 eV was observed after the graft polymerization after plasma treatment. According to the infrared absorption spectrum, after plasma graft polymerization, 1,180 cm -1 and 1,07
Absorption of the stretching vibration of S = O was recognized at 0 cm -1 . Further, scanning electron microscope observation confirmed the formation of a graft layer on the fibril structure of the poly (3-methylthiophene) film in plasma graft polymerization. From these results, it can be said that vinyl sulfonic acid was graft-polymerized on the surface of the poly (3-methylthiophene) film.
【００１３】〔参考例〕
プラズマグラフト重合したポリアニリン膜の酸化還元特
性：
（１）ビニルスルホン酸をプラズマグラフト重合したポ
リアニリン膜：実施例１及び実施例３で作製したプラズ
マグラフト重合ポリアニリン膜と未表面改質ポリアニリ
ン膜との酸化還元特性を比較した。電解液として過塩素
酸リチウム１．０ｍｏｌ／リットルの炭酸プロピレン溶
液、作用極にポリアニリン膜、対極にリチウム、参照電
極にＡｇ／ＡｇＣｌを用い、試験温度２０℃、走査電位
範囲−０．９〜＋１．０Ｖ、走査速度５ｍＶ／ｓｅｃで
サイクリックボルタモグラムを測定した。プラズマグラ
フト重合ポリアニリン膜と未表面改質ポリアニリン膜の
サイクリックボルタモグラムはほぼ一致し、酸化還元能
に変化はなかった。Ｘ線光電子スペクトルによれば、未
表面改質ポリアニリン膜では酸化後、還元後とも５５ｅ
ＶのＬｉ1Sピークは認められなかった。プラズマグラフ
ト重合ポリアニリン膜では酸化後はＬｉ1Sピークは認め
られなかったが、還元後ではＬｉ1Sピークが認められ
た。また、赤外線吸収スペクトルによれば、未表面改質
ポリアニリン膜では１，１００ｃｍ-1に現れるＣｌＯ4
- イオンのＣｌ−Ｏ伸縮運動の吸光度は、酸化後では大
きく還元後では小さくなった。しかし、プラズマグラフ
ト重合膜ではＣｌＯ 4 - イオンのＣｌ−Ｏ伸縮運動の吸
光度は、酸化後、還元後も殆ど変化しなかった。[Reference Example]
Redox characteristics of plasma-grafted polyaniline film
sex:
(1) Plasma-polymerized vinyl sulfonic acid
Lianiline film: Plas prepared in Examples 1 and 3
Magrafed polyaniline film and unmodified polyaniline
The oxidation-reduction characteristics of the film were compared. Perchlor as electrolyte
Lithium oxide 1.0 mol / liter propylene carbonate dissolved
Liquid, polyaniline film on working electrode, lithium on counter electrode, reference voltage
Ag / AgCl is used for the electrode, test temperature is 20 ° C, scanning potential
Range -0.9 to + 1.0V, scanning speed 5mV / sec
The cyclic voltammogram was measured. Plasmagrass
Ft-polymerized polyaniline film and unmodified surface polyaniline film
The cyclic voltammograms are almost the same, and the redox capacity is
Did not change. According to the X-ray photoelectron spectrum,
Surface modified polyaniline film is 55e after oxidation and after reduction
Li of V1SNo peak was observed. Plasma graph
After the oxidation, the Li-polymerized polyaniline film is Li1SAcknowledged peak
Was not obtained, but after reduction Li1SA peak is observed
It was In addition, according to the infrared absorption spectrum, unmodified surface
1,100 cm for polyaniline film-1Appearing in ClOFour
-The absorbance of Cl-O stretching motion of ions is large after oxidation.
It became smaller after Kiku reduction. But the plasmagraph
ClO for polymerized film Four -Absorption of Cl-O stretching motion of ions
The luminosity hardly changed after oxidation and reduction.
【００１４】（２）メタクリル酸でプラズマグラフト重
合したポリアニリン膜：実施例２で作製したプラズマグ
ラフト重合ポリアニリン膜と未表面改質ポリアニリン膜
との酸化還元特性を比較した。電解液として過塩素酸リ
チウム１．０ｍｏｌ／リットルの炭酸プロピレン溶液、
作用極にポリアニリン膜、対極にリチウム、参照電極に
Ａｇ／ＡｇＣｌを用い、試験温度２０℃、走査電位範囲
−０．９〜＋１．０Ｖ、走査速度５ｍＶ／ｓｅｃでサイ
クリックボルタモグラムを測定した。プラズマグラフト
重合ポリアニリン膜と未表面改質ポリアニリン膜のサイ
クリックボルタモグラムはほぼ一致し、酸化還元能に変
化はなかった。Ｘ線光電子スペクトルによれば、未表面
改質ポリアニリン膜では酸化後、還元後とも５５ｅＶの
Ｌｉ1Sピークは認められなかった。プラズマグラフト重
合ポリアニリン膜では酸化後はＬｉ1Sピークは認められ
なかったが、還元後ではＬｉ1Sピークが認められた。ま
た、赤外線吸収スペクトルによれば、未表面改質ポリア
ニリン膜では１，１００ｃｍ-1に現れるＣｌＯ4 - イオ
ンのＣｌ−Ｏ伸縮運動の吸光度は、酸化後では大きく還
元後では小さくなった。しかし、プラズマグラフト重合
膜ではＣｌＯ 4 - イオンのＣｌ−Ｏ伸縮運動の吸光度
は、酸化後、還元後も殆ど変化しなかった。(2) Plasma graft weight with methacrylic acid
Combined polyaniline film: plasma group prepared in Example 2
Raft polymerized polyaniline film and unsurface-modified polyaniline film
And the redox properties were compared. Perchloric acid as electrolyte
Propylene carbonate solution of 1.0 mol / l thium,
Polyaniline film as working electrode, lithium as counter electrode, and reference electrode
Using Ag / AgCl, test temperature 20 ℃, scanning potential range
-0.9 to +1.0 V, scan speed 5 mV / sec
The click voltammogram was measured. Plasma graft
The size of the polymerized polyaniline film and the unsurface-modified polyaniline film
The click voltammograms are almost the same, and the redox capacity is changed.
There was no change. According to X-ray photoelectron spectrum, unsurfaced
With the modified polyaniline film, 55 eV after oxidation and reduction
Li1SNo peak was observed. Plasma graft weight
In the combined polyaniline film, after oxidation, Li1SPeaks are observed
No, but after reduction Li1SA peak was observed. Well
In addition, according to the infrared absorption spectrum
1,100 cm for Nirin film-1Appearing in ClOFour -Io
The absorbance of Cl-O stretching motion of
It became smaller after the birth. However, plasma graft polymerization
ClO in the membrane Four -Absorbance of Cl-O stretching motion of ions
Was almost unchanged after oxidation and reduction.
【００１５】（３）プラズマグラフト重合したポリ（３
−メチルチオフェン）膜：実施例５で作製したプラズマ
グラフト重合ポリ（３−メチルチオフェン）膜と未表面
改質ポリ（３−メチルチオフェン）膜との酸化還元特性
を比較した。電解液として過塩素酸リチウム１．０ｍｏ
ｌ／リットルの炭酸プロピレン溶液、作用極にポリ（３
−メチルチオフェン）膜、対極にリチウム、参照電極に
Ａｇ／ＡｇＣｌを用い、試験温度２０℃、走査電位範囲
−０．４〜＋０．４Ｖ、走査速度５ｍＶ／ｓｅｃでサイ
クリックボルタモグラムを測定した。プラズマグラフト
重合ポリ（３−メチルチオフェン）膜と未表面改質ポリ
（３−メチルチオフェン）膜のサイクリックボルタモグ
ラムはほぼ一致し、酸化還元能に変化はなかった。Ｘ線
光電子スペクトルによれば、未表面改質ポリ（３−メチ
ルチオフェン）膜では酸化後、還元後とも５５ｅＶのＬ
ｉ1Sピークは認められなかった。プラズマグラフト重合
ポリ（３−メチルチオフェン）膜では酸化後はＬｉ1Sピ
ークは認められなかったが、還元後ではＬｉ1Sピークが
認められた。また、赤外線吸収スペクトルによれば、未
表面改質ポリ（３−メチルチオフェン）膜では１，１０
０ｃｍ-1に現れるＣｌＯ4 - イオンのＣｌ−Ｏ伸縮運動
の吸光度は、酸化後では大きく還元後では小さくなっ
た。しかし、プラズマグラフト重合ポリ（３−メチルチ
オフェン）膜ではＣｌＯ4 - イオンのＣｌ−Ｏ伸縮運動
の吸光度は、酸化後、還元後も殆ど変化しなかった。(3) Plasma graft polymerized poly (3
-Methylthiophene) film: The redox characteristics of the plasma graft-polymerized poly (3-methylthiophene) film prepared in Example 5 and the unsurface-modified poly (3-methylthiophene) film were compared. Lithium perchlorate 1.0mo as electrolyte
l / l propylene carbonate solution, poly (3
-Methylthiophene) film, lithium as a counter electrode, and Ag / AgCl as a reference electrode, cyclic voltammograms were measured at a test temperature of 20 ° C, a scanning potential range of -0.4 to +0.4 V, and a scanning speed of 5 mV / sec. The cyclic voltammograms of the plasma graft-polymerized poly (3-methylthiophene) film and the unsurface-modified poly (3-methylthiophene) film were almost the same, and the redox ability was unchanged. According to the X-ray photoelectron spectrum, the unsurface-modified poly (3-methylthiophene) film had an L of 55 eV after oxidation and after reduction.
No i 1S peak was observed. In the plasma graft polymerized poly (3-methylthiophene) film, no Li 1S peak was observed after oxidation, but a Li 1S peak was observed after reduction. In addition, according to the infrared absorption spectrum, the unsurface-modified poly (3-methylthiophene) film had 1,10
The absorbance of the Cl—O stretching motion of ClO 4 − ion appearing at 0 cm −1 was large after oxidation and small after reduction. However, the plasma graft polymerization of poly (3-methylthiophene) ClO 4 is a film - absorbance of ClO stretching movement of ions, after oxidation, did not substantially change after reduction.
【００１６】以上の（１）〜（３）の結果をまとめると
次のとおりである。イオン交換基を有する高分子鎖で表
面をグラフトさせる前後のポリアニリン膜及びポリ（３
−メチルチオフェン）膜の酸化還元能に変化はなかっ
た。しかし、Ｘ線光電子スペクトルによれば、プラズマ
グラフト重合前では酸化後、還元後とも５５ｅＶのＬｉ
1Sピークは認められなかったのに対し、プラズマ重合後
では酸化後はＬｉ1Sピークは認められなかったが、還元
後ではＬｉ1Sピークは認められた。また、赤外線吸収ス
ペクトルによれば、プラズマグラフト重合前では１，１
００ｃｍ-1に現れるＣｌＯ4 - イオンのＣｌ−Ｏ伸縮運
動の吸光度は、酸化後では大きく還元後では小さくなっ
たが、プラズマグラフト重合後ではＣｌＯ4 - イオンの
Ｃｌ−Ｏ伸縮運動の吸光度は酸化後、還元後も殆ど変化
しなかった。これらの結果は、プラズマ重合前はポリア
ニリン膜及びポリ（３−メチルチオフェン）膜の酸化・
還元によりＣｌＯ4 - イオンの出入りが起こるが、プラ
ズマグラフト重合後はポリアニリン膜及びポリ（３−メ
チルチオフェン）膜の酸化・還元によりＣｌＯ4 - イオ
ンの出入りが起こるのではなく、Ｌｉイオンの出入りが
起こっていることを示しており、明らかにプラズマグラ
フト重合により酸化・還元の際の駆動イオンを変化させ
たと言える。The results of the above (1) to (3) are summarized as follows. Before and after grafting the surface with a polymer chain having an ion-exchange group, polyaniline film and poly (3
There was no change in the redox ability of the -methylthiophene) film. However, according to the X-ray photoelectron spectrum, before the plasma graft polymerization, the Li of 55 eV was obtained both after the oxidation and after the reduction.
While 1S peak was not observed, but after the plasma polymerization after oxidation was observed Li 1S peak, Li 1S peak after reduction was observed. Further, according to the infrared absorption spectrum, 1,1 before plasma graft polymerization
Appears at 00cm -1 ClO 4 - absorbance of ClO stretching movement of ions, became smaller after large reduction after oxidation, ClO 4 in after plasma graft polymerization - absorbance of ClO stretching movement of ions oxidation After that, there was almost no change after the reduction. These results indicate that the polyaniline film and poly (3-methylthiophene) film were
The reduction causes ClO 4 − ions to move in and out, but after plasma graft polymerization, ClO 4 − ions do not move in and out due to the oxidation and reduction of the polyaniline film and the poly (3-methylthiophene) film, but the Li ions move in and out. It can be said that the driving ions at the time of oxidation / reduction are changed by plasma graft polymerization.
【００１７】[0017]
【発明の効果】以上のように、本発明に係る表面改質さ
れた導電性高分子化合物を用いてリチウムバッテリーを
構成した場合、従来は導電性高分子化合物内部にアニオ
ンが出入りして充放電していたものが、カチオンが導電
性高分子内に出入りして充放電が行われるようになり、
これまではアニオンを溶解させるために必要であった電
解液が必要なくなる。従ってカチオンが透過するのに必
要な電解液だけあればバッテリーが構成できるようにな
る。このため、不必要になった電解液分だけのバッテリ
ーの軽量化が可能となり、高エネルギー密度のポリマー
リチウムバッテリーが実現可能となる。本発明は、上記
リチウムバッテリーに限らず、カチオン又はアニオンの
どちらか一方を選択的に透過させたい導電性高分子から
なる電極を作製する有効な手段である。従って、本発明
のイオン交換基を表面に有する導電性高分子は、導電性
高分子内部への選択的イオン透過方法として有効であ
り、また得られるイオン交換基表面修飾導電性高分子は
高エネルギー密度の高分子バッテリー用電極として、及
び光電池、電子素子、半導体素子等の電極として利用可
能である。As described above, when a lithium battery is constructed using the surface-modified conductive polymer compound according to the present invention, conventionally, anions enter and leave the conductive polymer compound to charge and discharge. What had been done, cations came in and out of the conductive polymer, and charging and discharging began,
The electrolyte solution that was required to dissolve the anions up to now is no longer necessary. Therefore, a battery can be constructed with only the electrolytic solution necessary for cation permeation. Therefore, the weight of the battery can be reduced by the amount of unnecessary electrolyte, and a polymer lithium battery with high energy density can be realized. INDUSTRIAL APPLICABILITY The present invention is not limited to the above-mentioned lithium battery, and is an effective means for producing an electrode made of a conductive polymer which is desired to selectively permeate either cation or anion. Therefore, the electroconductive polymer having an ion-exchange group on the surface of the present invention is effective as a method of selectively permeating ions into the electroconductive polymer, and the obtained ion-exchange group surface-modified electroconductive polymer has high energy. It can be used as an electrode for high density polymer batteries and as an electrode for photovoltaic cells, electronic devices, semiconductor devices and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 橋爪 克浩 神奈川県横浜市金沢区幸浦一丁目８番地 １ 三菱重工業株式会社基板技術研究所 内 (72)発明者 田坂 佳之 神奈川県横浜市金沢区幸浦一丁目８番地 １ 三菱重工業株式会社基板技術研究所 内 (56)参考文献 特開 平６−32845（ＪＰ，Ａ) 特開 平７−126526（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 283/00 C08F 2/00 H01M 4/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiro Hashizume 1-8, Koura, Kanazawa-ku, Yokohama-shi, Kanagawa 1 Substrate Technology Laboratory, Mitsubishi Heavy Industries, Ltd. (72) Yoshiyuki Tasaka, Koichi-ura, Kanazawa-ku, Yokohama, Kanagawa 8-chome 1 Mitsubishi Heavy Industries, Ltd. Substrate Technology Laboratory (56) References JP-A-6-32845 (JP, A) JP-A-7-126526 (JP, A) (58) Fields investigated (Int.Cl . 7 , DB name) C08F 283/00 C08F 2/00 H01M 4/00
Claims (2)
不活性ガス雰囲気下でプラズマ照射した後、イオン交換
基を有する高分子をグラフト重合させることを特徴とす
る導電性高分子化合物膜の製造方法。1. A surface of a film made of a conductive polymer compound
Ion exchange after plasma irradiation in an inert gas atmosphere
Characterized by graft polymerizing a polymer having a group
A method for producing a conductive polymer compound film .
相法によるものであることを特徴とする請求項１記載の
導電性高分子化合物膜の製造方法。2. The above-mentioned graft polymerization is a liquid phase method and / or gas.
The method according to claim 1, wherein the phase method is used.
A method for producing a conductive polymer compound film .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26248994A JP3453200B2 (en) | 1994-10-26 | 1994-10-26 | Method for producing surface-modified conductive polymer compound film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26248994A JP3453200B2 (en) | 1994-10-26 | 1994-10-26 | Method for producing surface-modified conductive polymer compound film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08120033A JPH08120033A (en) | 1996-05-14 |
| JP3453200B2 true JP3453200B2 (en) | 2003-10-06 |
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ID=17376510
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| JP26248994A Expired - Fee Related JP3453200B2 (en) | 1994-10-26 | 1994-10-26 | Method for producing surface-modified conductive polymer compound film |
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| KR100345289B1 (en) * | 1999-09-16 | 2002-07-25 | 한국과학기술연구원 | Development of polymer surface modification by hydrogen ion assisted reaction |
| KR20020021675A (en) * | 2000-06-01 | 2002-03-21 | 박호군 | Method of modifying a surface of polymer membrane by ion assisted reaction |
| US20140311347A1 (en) * | 2011-12-01 | 2014-10-23 | The Regents Of The University Of California | Polaniline based membranes for separation of carbon dioxide and methane |
| GB201215098D0 (en) * | 2012-08-24 | 2012-10-10 | Fujifilm Mfg Europe Bv | Method of treating a porous substrate and manufacture of a membrane |
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