전도성 Polypyrrole의 분해 특성과 물성 개선

이홍기; 엄정호; 박수길; 심미자; 김상욱; 이주성

Journal of the Korean Industrial and Engineering Chemistry, Vol.5, No.5, 764-771, October, 1994

Export Citation

전도성 Polypyrrole의 분해 특성과 물성 개선

Characteristics of Degradation and Improvement of Properties with Conducting Polypyrrole

이홍기, 엄정호, 박수길, 심미자, 김상욱, 이주성

초록

친핵성용매하에서 p-toluenesulfonic acid나 bezensulfonic acid와 같은 유기산을 지지전해질 겸 dopant로 사용하여 전도성 Polypyrrole필름을 전해중합하였고 분해 특성과 기계적 물성증가에 대하여 고찰하였다. Dimethyformamide/p-toluenesulfonic acid에서 합성한 polypyrrole 필름이 전도도 10-40S/cm, 인장강도 25N/mm². 연신율은 10%로 가장 좋은 특성을 나타내었다. 또한 전해중합시 최적 조건은 0.5M의 pyrrole과 0.5M의 p-toluenesulfonic acid를 첨가하여 정전류법에서는 2mA/cm²의 전류밀도가, 정전위법으로는 0.9V vs. Ag/Ag⁺에서 중합할 때였으며 생성된 필름은 공기중에서 안정하였고 도핑, 탈-도핑이 가역적이어서 2차 전지로서의 특성을 갖고 있었다 온도에 따른 분해과정이 1차 반응으로 dopant 음이온이 분해반응에 관여하지 않아 산화안정성이 좋았으며 분해활성화 에너지는 1.01JK^-1mol^-1, 25℃에서의 분해속도상수는 3.1×10^-7min^-1였다. 여러 가지 host polymer와의 composite를 검토한 결과 인장강도는 50%, 연신율은 100% 정도로 기계적 물성을 증가시킬 수 있었다.

Electrochemical synthesis of conductive polypyrrole films was carried out in nucleophilic solvent containing p-toluenesulfonic acid or bezensulfonic acid as supporting electrolyte and dopant. Also characteristics of degradation and improvement of mechanical properties were studied. The conductivity, tensile strength and elongation of the films obtained in dimethyformamide/p-toluenesulfonic acid had the highest value of 10-40S/cm, 25N/mm² and 10%, respectively. The optimum condition of electrochemical synthesis was 2mA/cm² for constant current method and 0.9V for constant potential method containing 0.5M pyrrole and 0.5M p-TSA. The obtained films showed good stability in air and electrode characteristics of secondary battery by reversibility in doping and undoping. The degradation process was 1st order reaction at various temeprature. The activation energy and rate constant of degradation reaction were 1.01JK^-1mol^-1 and 3.1×10^-7min^-1 respectively at 25℃. For the improvement of mechanical properties, composition of polypyrrole films with various host polymer were investigated and increase of tensile strength and elongation was confirmed.

[References]

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[1] Diaz JF, Crowley JI, Bargon J, Gardini GP, Torrance B, J. Electroanal. Chem., 121, 355 (1981)

[2] Genies E, Bidan G, Diaz A, J. Electrochem. Soc., 149(101), 1685 (1982)

[3] Prejza J, Lundstorm I, Skotheim T, J. Electrochem. Soc., 129, 1685 (1982)

[4] Bull RA, Fan FR, Bard AJ, J. Electrochem. Soc., 130, 1936 (1983)

[5] Nazzal A, Street GB, J. Chem. Soc.-Chem. Commun., 84 (1983)

[6] Blinc ER, Burger M, Lozar B, Seliger J, Slak J, Rutar V, Arend H, Kind R, J. Chem. Phys., 66, 278 (1977)

[7] Salmon M, Diaz AF, Logan AJ, Krounbi M, Bergon J, Mol. Cryst., 83, 1297 (1983)

[8] Diaz AF, J. Chem. Soc.-Chem. Commun., 635 (1979)

[9] Skotheim TA, "Handbook of Conducting Polymers," 81, Marcel Dekker, New York (1986)

[10] Diaz AF, Lacroix JC, 高分子, 36, 278 (1987)

[11] Bates N, Cross M, Lines R, Walton D, J. Chem. Soc.-Chem. Commun., 871 (1985)

[12] Song GS, Lee HK, Shin SH, Lee JS, Polym.(Korea), 14(2), 97 (1990)

[13] Samuelson LA, Druy MA, Macromolecules, 19, 824 (1986)

[14] Salmon M, Diaz AF, Logan AJ, Krounbi M, Bargon J, Mol. Cryst. Liq. Cryst., 83, 265 (1982)