Abstract
The kinetics of the electroreduction of O2 in the (Li0.62K0.38)2CO3 eutectic melt on the oxide electrode prepared of in situ lithiated LaCoO3 – δ is studied. Superoxide ions and molecular oxygen are shown to be the major electroactive particles under the studied conditions, which correlates with the investigations on a gold electrode. The reaction mechanism on the oxide electrode differs from the mechanisms proposed for the gold electrode. Several mechanisms are proposed to take into account the specificity of the oxide electrode. The exchange current densities are found to be independent of the partial oxygen pressure and to vary in a range of 220–290 mA/cm2 depending on the experimental conditions and the operating mechanism.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
M. Franke and J. Winnick, “A high performance molten carbonate fuel cell cathode,” J. Appl. Electrochem. 119 (1), 1–9 (1989).
P. Ganesan, H. Colon, B. Haran, and B. N. Popov, “Performance of La0.8Sr0.2CoO3 coated NiO as cathodes for molten carbonate fuel cells,” J. Power Sources 115 (1), 12–18 (2003).
B. Huang, W. Shao-rong, Y. Qing-chun, L. Yu, and H. Ke-Ao, “Electrochemical characterization of La0.8Sr0.2MnO3-coated NiO as cathodes for molten carbonate fuel cells,” J. Appl. Electrochem. 135 (11), 1145–1156 (2005).
S. A. Song, S. C. Jang, J. Han, S. P. Yoon, S. W. Nam, I. H. Oh, and T. H. Lim, “Enhancement of cell performance using a gadolinium strontium cobaltite coated cathode in molten carbonate fuel cells,” J. Power Sources 196 (23), 9900–9905 (2011).
Y. Gong, X. Li, L. Zhang, W. Tharp, C. Qin, and K. Huang, “Promoting electrocatalytic activity of a composite SOFC cathode La0.8Sr0.2MnO3–δ/Ce0.8Gd0.2O2–δ with molten carbonates,” J. Electrochem. Soc. 161 (3), F226–F232 (2014).
M. Anderson and Y. S. Lin, “Carbonate–ceramic dualphase membrane for carbon dioxide separation,” J. Membr. Sci. 357 (1–2), 122–129 (2010).
C. E. Baumgartner, R. H. Arendt, C. D. Iacovangelo, and B. R. Karas, “Molten carbonate fuel cell cathode materials study,” J. Electrochem. Soc. 131 (10), 2217–2221 (1984).
C. Y. Yuh and J. R. Selman, “Polarization of the molten carbonate fuel cell anode and cathode,” J. Electrochem. Soc. 131 (9), 2062–2069 (1984).
H. Morita, M. Komoda, Y. Mugikura, Y. Izaki, T. Watanabe, Y. Masuda, and T. Matsuyama, “Performance analysis of molten carbonate fuel cell using a Li/Na electrolyte,” J. Power Sources 112 (2), 509–518 (2002).
R. C. Makkus, K. Hemmes, and J. H. W. de Wit, “A comparative study of NiO(Li), LiFeO2, and LiCoO2 porous cathodes for molten carbonate fuel cells,” J. Electrochem. Soc. 141 (12), 3429–3438 (1994).
S. I. Vecherskii, M. A. Konopel’ko, and N. N. Batalov, “Equilibrium concentration of electroactive particles in molten (Li0.62K0.38)2CO3 and mechanisms of oxygen reduction on the gold electrode,” Elektrokhim. Energetika 11 (3), 120–127 (2011).
S. I. Vecherskii, M. A. Konopel’ko, and N. N. Batalov, “Catalytic activity of the LaLi0.1Co0.1Fe0.8O3–δ cathode in molten (Li0.62K0.38)2CO3: I. Experimental results and equivalent electrical scheme of an oxide–melt contact,” Elektrokhim. Energetika 14 (1), 11–18 (2014).
S. I. Vecherskii, M. A. Konopel’ko, and N. N. Batalov, “Catalytic activity of the LaLi0.1Co0.1Fe0.8O3–δ cathode in molten (Li0.62K0.38)2CO3: II. Reaction mechanisms and catalytic activity of an oxide electrode,” Elektrokhim. Energetika 14 (1), 19–25 (2014).
J. A. Prins-Jansen, K. Hemmes, and J. H. W. de Wit, “An extensive treatment of the agglomerate model for porous electrodes in molten carbonate fuel cells: I. Qualitative analysis of the steady-state model,” Electrochim. Acta 42 (23–24), 3585–3600 (1997).
P. Delahay, “A new electroanalysis method: coulostatic or charge-step method,” Anal. Chim. Acta 27, 90–93 (1962).
G. Wilemski, “Simple porous models for carbonate fuel cells,” J. Electrochem. Soc. 130 (1), 117–121 (1983).
A. L. Rotinyan, K. I. Tikhonov, and I. A. Shoshina, Theoretical Electrochemistry, Ed. by A. L. Rotinyan (Khimiya, Leningrad, 1981).
M. Enyo and T. Yokoyama, “The reaction order and general equations for electrode kinetics,” Electrochim. Acta 16, 223–243 (1971).
M. A. Konopel’ko, N. N. Batalov, and N. O. Esina, “Electrochemical activity of solid solutions La1–xSrxCoO3 in the oxygen electroreduction in carbonate melts,” Elektrokhimiya 36 (11), 1241–1245 (2000).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © S.I. Vecherskii, M.A. Konopel’ko, N.N. Batalov, M.A. Zvezdkin, I.V. Zvezdkina, 2018, published in Rasplavy, 2018, No. 1, pp. 38–50.
Rights and permissions
About this article
Cite this article
Vecherskii, S.I., Konopel’ko, M.A., Batalov, N.N. et al. LaCoO3 – δ as the Material of an Oxygen Electrode for a Molten Carbonate Fuel Cell: II. Catalytic Activity of LaCoO3 – δ for the Electroreduction of Oxygen in Molten (Li0.62K0.38)2CO3. Russ. Metall. 2018, 155–162 (2018). https://doi.org/10.1134/S0036029518020210
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036029518020210