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Structure, conductivity and redox reversibility of Ca-doped cerium metavanadate

Petit, Christophe T. G. and Lan, Rong and Cowin, Peter I. and Irvine, John T. S. and Tao, Shanwen (2011) Structure, conductivity and redox reversibility of Ca-doped cerium metavanadate. Journal of Materials Chemistry, 21 (24). pp. 8854-8861. ISSN 0959-9428

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A-site substituted cerium metavanadates, Ce1-xCaxVO3, were synthesised by solid-state reactions from single-phase powders of the corresponding orthovanadates. All metavanadate samples were found to exhibit either an orthorhombic and/or monoclinic phase of space group Pnma (62) with a = 5.5067 (4), b = 7.7904 (5) and c = 5.4814(7) angstrom for Ce0.8Ca0.2VO3. X-Ray diffraction patterns and thermal analyses have shown that the reduction of Ca-doped CeVO3 from the equivalent orthovanadate is redox phase reversible without formation of parasitic phases at x = 0.2, 0.3. Conductivity measurements were performed in air and in dry 5% H-2-Ar with conductivity of Ce1-xCaxVO3 ranging from 1.5 to 13 S cm(-1) at 700 degrees C in a reducing atmosphere. Sample Ce0.7Ca0.3VO3 exhibits the highest conductivity in a reducing atmosphere in all the measured samples which could be a potential anode or as a part of composite anode for SOFCs. The conductivity of Ce0.7Ca0.3VO3 is higher than that for Ce0.85Sr0.15VO3 which could be related to the higher doping level.