피롤/아닐린 고분자 복합체의 전기화학적 성질

차성극

Polymer(Korea), Vol.22, No.3, 400-407, May, 1998

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피롤/아닐린 고분자 복합체의 전기화학적 성질

Electrochemical Properties of Pyrrole/Aniline Polymer Composite

차성극

초록

피롤고분자(ppy)와 아닐린고분자(pan)로 된 두 성분의 고분자 복합체 전극을 전기화학적 방법으로 제작하기 위하여, 먼저 다공성 ppy피막을 백금(Pt)위에 중합한 후 그 다공성 피막내에 pan을 그 조성이 10-35%되게 끼워심기 중합하여 이 피막의 전기적 성질들을 개선시켰다. 이 때 전기적 중합속도를 Pt, Pt위에 ppy를 1.70 Ccm^-2량으로 입힌 Pt/ppy, 그리고 Pt위에 Pan을 0.1130 Ccm^-2 만큼 입힌 Pt/pan 회전판 전극들에서 측정하였다. 그 값은 Pt/ppy 전극에서 2.67×10^-5cm/s로 Pt/pan 전극의 2.30 x 10^-7cms^-1보다 백배이상 크게 나타났다. Pt/ppy/pan (x) 전극의 순환전압 전류 특성은 고분자 가닥들의 polaron자리에 도핑된 이온이 ClO₄^-일 때보다 PF₆^-일 때 더 뚜렷하였다. 아닐린고분자 함량(x)이 0.2일 때 이 피막의 도핑준위가 52%까지 증가하였으며, 도핑/탈도핑 효율은 88%였고, 전기전도도는 x가 0.35일 때 331 Scm^-1으로 ppy만일 때보다 다섯배나 증가하였다. 그러나 cyclability는 ppy만으로 된 경우에 비하여 75%까지 감소하였다.

Bi-Polymer film electrodes of Polypyrrole (ppy) and Polyaniline (pan) were prepared by electrochemical implantation into Porous ppy matrix with pan as level of 10 to 35% in order to improve the electrical properties. The rate constants of electropolymerization reactions were measured with smooth Pt, Pt covered with ppy (Pt/ppy), and Pt covered with pan (Pt/pan) of modified rotating disk electrode. The electropolymerization rate of pan polymer was faster on the Pt/ppy electrode as 2.67 x 10^-5 cms^-1 by a factor of hundred than 2.30×10^-7 cms^-1 of the Pt/pan. Cyclic voltammograms of Pt/ppy/pan (x) electrodes were quite different with the doping ions which were ClO₄^- and PF₆^-. The characteristic properties of redox reaction were more obvious at doped with PF₆^- ion. The amount of Pan in the ppy matrix enhanced the doping level of the electrode to 52% at pan content (x) of 0.2, doping/undoping efficiency to 88%, and the conductivity of the ppy/pan was 331 Scm^-1 at x = 0.35. However the cyclability was reduced by 75%, relative to PPy alone.

Keywords:electropolymerization;polypyrrole;polyaniline;polymer composite;dopant

[References]

Skotheim TA, "Handbook of Conducting Polymers," Mercel Dekker Inc., vol. 1, Chap 3 (1986)
Clarke JC, Scott JC, Street GB, IBM J. Res. Dev. B, 27, 313 (1983)
Bredas C, Scott JC, Yahushi K, Street GB, Phys. Rev., B, Condens. Matter, 30, 1023 (1984)
"Encyclopedia of Polymer Science & Engineering," vol. 13, p. 42, John Wiley & Sons, 2nd Ed. (1988)
Osaka T, Naoi K, Ogano S, J. Electrochem. Soc., 135, 1071 (1988)
Street GB, Lindsey SE, Nazzal AI, Wynne KJ, Mol. Cryst. Liq. Cryst., 118, 137 (1985)
Bargan J, Mahmand S, Waltman RJ, IBM J. Res. Dev., 27, 330 (1983)
Cha SK, Chung JJ, Cha CK, Abruna HD, J. Mater. Sci., 28, 6115 (1993)
Yang R, Evans DF, Christansen L, Hendrickson WA, J. Phys. Chem., 94, 6117 (1990)
Naoi K, Dsaka T, J. Electrochem. Soc., 134, 2479 (1987)
Yaysuda Y, Sakai H, Sgano S, J. Chem. Soc. Jpn., 7, 1331 (1985)
Osaka T, Naoi K, Sakai H, Ogano S, J. Electrochem. Soc., 134, 285 (1987)
Cha SK, Choi KS, Ahn BK, Kang SJ, J. Korean Chem. Soc., 40, 467 (1996)
Cha SK, J. Polym. Sci. B: Polym. Phys., 35(1), 165 (1997)
Diaz AF, Kanazawa K, J. Chem. Soc.-Chem. Commun., 635 (1979)
Focke WW, Whek GE, Wei Y, J. Phys. Chem., 91, 5813 (1987)
Macero DJ, Janeiro RA, Anal. Chem., 27, 585 (1962)
Wei Y, Sun Y, Tang X, J. Phys. Chem., 93, 4878 (1989)

[Referenced By]

[1] Skotheim TA, "Handbook of Conducting Polymers," Mercel Dekker Inc., vol. 1, Chap 3 (1986)

[2] Clarke JC, Scott JC, Street GB, IBM J. Res. Dev. B, 27, 313 (1983)

[3] Bredas C, Scott JC, Yahushi K, Street GB, Phys. Rev., B, Condens. Matter, 30, 1023 (1984)

[4] "Encyclopedia of Polymer Science & Engineering," vol. 13, p. 42, John Wiley & Sons, 2nd Ed. (1988)

[5] Osaka T, Naoi K, Ogano S, J. Electrochem. Soc., 135, 1071 (1988)

[6] Street GB, Lindsey SE, Nazzal AI, Wynne KJ, Mol. Cryst. Liq. Cryst., 118, 137 (1985)

[7] Bargan J, Mahmand S, Waltman RJ, IBM J. Res. Dev., 27, 330 (1983)

[8] Cha SK, Chung JJ, Cha CK, Abruna HD, J. Mater. Sci., 28, 6115 (1993)

[9] Yang R, Evans DF, Christansen L, Hendrickson WA, J. Phys. Chem., 94, 6117 (1990)

[10] Naoi K, Dsaka T, J. Electrochem. Soc., 134, 2479 (1987)

[11] Yaysuda Y, Sakai H, Sgano S, J. Chem. Soc. Jpn., 7, 1331 (1985)

[12] Osaka T, Naoi K, Sakai H, Ogano S, J. Electrochem. Soc., 134, 285 (1987)

[13] Cha SK, Choi KS, Ahn BK, Kang SJ, J. Korean Chem. Soc., 40, 467 (1996)

[14] Cha SK, J. Polym. Sci. B: Polym. Phys., 35(1), 165 (1997)

[15] Diaz AF, Kanazawa K, J. Chem. Soc.-Chem. Commun., 635 (1979)

[16] Focke WW, Whek GE, Wei Y, J. Phys. Chem., 91, 5813 (1987)

[17] Macero DJ, Janeiro RA, Anal. Chem., 27, 585 (1962)

[18] Wei Y, Sun Y, Tang X, J. Phys. Chem., 93, 4878 (1989)