네자리 Schiff base 금속(II) 착물들에 의한 LiAlCl<sub>4</sub>/SOCl<sub>2</sub> 전지의 전기촉매 효과에 대한 연구

심우종; 정병구; 나기수; 조기형; 최용국

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.3, 416-423, June, 1996

Export Citation

네자리 Schiff base 금속(II) 착물들에 의한 LiAlCl₄/SOCl₂ 전지의 전기촉매 효과에 대한 연구

Studies on electrocatalytic effects of LiAlCl₄/SOCl₂ cell by tetradentate Schiff base metal(II) complexes

심우종, 정병구, 나기수, 조기형, 최용국

초록

Co(II), Ni(II), Cu(II) 및 Mn(II)의 네자리 Schiff base 전이금속 화합물들이 첨가된 1.5 M LiAlCl₄/SOCl₂ 전해질 용액에서 SOCl₂에 관한 전기 화학적 환원 반응을 조사하였다. 이들 전이 금속(II) 착물들은 먼저 전극 표면에 흡착된 후 촉매로써 작용하였으며, 각각의 전이 금속(II) 착물들의 촉매 화합물에 대해 SOCl₂를 환원시킬 수 있는 최적 조건의 농도를 나타냈다. 촉매가 첨가된 전해질 용액에서 SOCl₂의 환원 반응에 대한 환원 전류는 최고 150% 정도 증가하였다. 주사 속도가 증가함에 따라 SOCl₂의 환원 전류는 증가하였고 환원 전위는 음 전위 방향으로 이동되었으며, SOCl₂의 환원 과정은 확산 지배적인 반응으로 진행되었다.

Electrochemical reduction of thionyl chloride in 1.5 M LiAlCl₄/SOCl₂ electrolyte solution containing tetradentate Schiff base Co(II), Ni(II), Cu(II), and Mn(II) complexes has been investigated at the glassy carbon electrode. The catalyst molecules of transition metal(II) complexes were adsorbed on the electrode surface and reduced thionyl chloride resulting in a generation of oxidized catalyst molecules. There was an optimum concentration for each catalyst compound. The current density of SOCl₂ reduction was enhanced up to 150% at the catalyst contained electrolyte solution. The reduction currents of thionyl chloride were increased and the reduction potentials were shifted to the negative potential as scan rates became faster. The reduction of thionyl chloride was proceeded to diffusion controlled reaction.

[References]

Auborn JJ, French KW, Lieberman SI, Shah VK, Heller A, J. Electrochem. Soc., 120, 6313 (1973)
Ehl WK, Christopusous JA, Ramirez M, Gilman S, J. Electrochem. Soc., 120, 1619 (1973)
Auborn JJ, Bezman RD, French KW, Heller A, Lieberman SI, Proc. 16th Power Sources Symp., 26, 45 (1974)
Blomgren GE, Leger VZ, Kronenberg ML, Kalnoki-Kis T, Brodd RJ, Power Sources, 7, Proceedings of the 11th International Power Sources Symposium, J. Thomson, Ed., 583, Academic Press, New York (1978)
Dey AN, Thin Solid Films, 43, 131 (1977)
Borden WL, Dey AN, J. Electrochem. Soc., 126, 2035 (1979)
Borden WL, Dey AN, J. Electrochem. Soc., 127, 1419 (1980)
Abraham KM, Mank RM, J. Electrochem. Soc., 127, 2091 (1980)
Venkatasethy HV, Saathoff DJ, J. Electrochem. Soc., 128, 773 (1981)
Istone WK, Brodd RJ, J. Electrochem. Soc., 129, 1853 (1980)
Venkatasetty HV, Szpak S, J. Chem. Eng. Data, 28, 47 (1983)
Delick FM, Cieslak WR, Sandia Report (1985)
Dampier FW, Cole TA, J. Electrochem. Soc., 135, 938 (1986)
Atkins P, hefter GT, Singh P, J. Power Sources, 36, 17 (1991)
Nagaura T, Tozawa K, Prog. Batteries Sol. Cells, 9 (1990)
Gabano JP, "Lithium Batteries," Academic Press, New York (1983)
Baturina OA, J. Power Sources, 36, 127 (1991)
Abraham KM, J. Power Sources, 34, 81 (1991)
Abraham KM, Electrochim. Acta, 37, 531 (1992)
Harris WS, Thesis, University of California, Berkeley (1958)
Jasinski R, "High Energy Batteries," Plenum Press, New York (1967)
Doddapaneni N, J. Electrochem. Soc., 86(12), 630 (1986)
Ashmawy FM, McAwiffe CA, Parish RV, Tames J, J. Chem. Soc.-Dalton Trans., 1391 (1985)
Chjo KH, Choi YK, Lee SJ, Kim CY, Lim CP, J. Korean Chem. Soc., 36, 5 (1992)
Doddapaneni N, Proceed. Symp. Lithium Batteries, 84(1), 122 (1984)
Doddapaneni N, J. Electrochem. Soc., 81(1), 83 (1981)
Doddapaneni N, J. Electrochem. Soc., 81(2), 583 (1981)
Doddapaneni N, Proceed. Symp. Electrochem. Soc., 84(12), 630 (1986)
Choi YK, Kim BS, Park SM, J. Electrochem. Soc., 140, 11 (1993)
Choi YK, Park SM, Delnick FM, Doddapaneni N, J. Electrochem. Soc., submitted (1995)
Doddapaneni N, Proc. 32nd Power Symp., 525 (1986)
Madou MJ, Smith JJ, Szpak S, J. Electrochem. Soc., 134, 2794 (1987)
Bernstein PA, Lever ABP, Inorg. Chem., 29, 608 (1990)
Bard AJ, Faulkner LR, "Electrochemical Methods," John Wiley & Sons, New York, Chap. 6 (1980)
Chiu JG, Wang YY, Wan CC, J. Power Sources, 21, 119 (1987)
Pyun CH, Park SM, Anal. Chem., 58, 251 (1986)

[1] Auborn JJ, French KW, Lieberman SI, Shah VK, Heller A, J. Electrochem. Soc., 120, 6313 (1973)

[2] Ehl WK, Christopusous JA, Ramirez M, Gilman S, J. Electrochem. Soc., 120, 1619 (1973)

[3] Auborn JJ, Bezman RD, French KW, Heller A, Lieberman SI, Proc. 16th Power Sources Symp., 26, 45 (1974)

[4] Blomgren GE, Leger VZ, Kronenberg ML, Kalnoki-Kis T, Brodd RJ, Power Sources, 7, Proceedings of the 11th International Power Sources Symposium, J. Thomson, Ed., 583, Academic Press, New York (1978)

[5] Dey AN, Thin Solid Films, 43, 131 (1977)

[6] Borden WL, Dey AN, J. Electrochem. Soc., 126, 2035 (1979)

[7] Borden WL, Dey AN, J. Electrochem. Soc., 127, 1419 (1980)

[8] Abraham KM, Mank RM, J. Electrochem. Soc., 127, 2091 (1980)

[9] Venkatasethy HV, Saathoff DJ, J. Electrochem. Soc., 128, 773 (1981)

[10] Istone WK, Brodd RJ, J. Electrochem. Soc., 129, 1853 (1980)

[11] Venkatasetty HV, Szpak S, J. Chem. Eng. Data, 28, 47 (1983)

[12] Delick FM, Cieslak WR, Sandia Report (1985)

[13] Dampier FW, Cole TA, J. Electrochem. Soc., 135, 938 (1986)

[14] Atkins P, hefter GT, Singh P, J. Power Sources, 36, 17 (1991)

[15] Nagaura T, Tozawa K, Prog. Batteries Sol. Cells, 9 (1990)

[16] Gabano JP, "Lithium Batteries," Academic Press, New York (1983)

[17] Baturina OA, J. Power Sources, 36, 127 (1991)

[18] Abraham KM, J. Power Sources, 34, 81 (1991)

[19] Abraham KM, Electrochim. Acta, 37, 531 (1992)

[20] Harris WS, Thesis, University of California, Berkeley (1958)

[21] Jasinski R, "High Energy Batteries," Plenum Press, New York (1967)

[22] Doddapaneni N, J. Electrochem. Soc., 86(12), 630 (1986)

[23] Ashmawy FM, McAwiffe CA, Parish RV, Tames J, J. Chem. Soc.-Dalton Trans., 1391 (1985)

[24] Chjo KH, Choi YK, Lee SJ, Kim CY, Lim CP, J. Korean Chem. Soc., 36, 5 (1992)

[25] Doddapaneni N, Proceed. Symp. Lithium Batteries, 84(1), 122 (1984)

[26] Doddapaneni N, J. Electrochem. Soc., 81(1), 83 (1981)

[27] Doddapaneni N, J. Electrochem. Soc., 81(2), 583 (1981)

[28] Doddapaneni N, Proceed. Symp. Electrochem. Soc., 84(12), 630 (1986)

[29] Choi YK, Kim BS, Park SM, J. Electrochem. Soc., 140, 11 (1993)

[30] Choi YK, Park SM, Delnick FM, Doddapaneni N, J. Electrochem. Soc., submitted (1995)

[31] Doddapaneni N, Proc. 32nd Power Symp., 525 (1986)

[32] Madou MJ, Smith JJ, Szpak S, J. Electrochem. Soc., 134, 2794 (1987)

[33] Bernstein PA, Lever ABP, Inorg. Chem., 29, 608 (1990)

[34] Bard AJ, Faulkner LR, "Electrochemical Methods," John Wiley & Sons, New York, Chap. 6 (1980)

[35] Chiu JG, Wang YY, Wan CC, J. Power Sources, 21, 119 (1987)

[36] Pyun CH, Park SM, Anal. Chem., 58, 251 (1986)