Nonstoichiometry and Defect Chemistry of Ceria Solid Solutions

Ceria solid solutions are potential electrolytes for solid oxidefuel cells (SOFC). At the anode side of SOFCs at low oxygen partialpressures ceria is partially reduced. The nonstoichiometry ofCeO2-x solid solutions with 20 mol%SmO1.5, 20 mol% GdO1.5 and 10 mol%CaO were investigated by isothermal coulometric titration in a zirconia cellin the temperature range from 700 to 900°C and in the oxygen partialpressure range from 10-12 to 10-25 atm. Theresults of the 3 different compositions at 900°C are comparable to thosefor pure ceria. At lower temperatures, pure ceria is more stable againstreduction than ceria solid solutions. The dependence of nonstoichiometry onoxygen partial pressure suggests a defect model with oxygen vacancies andtheir associates with reduced cerium cations and dopant cations. Low oxygennonstoichiometries of x = 0.005 to 0.008 can be expected for ceria solidsolutions at 700° under SOFC operating conditions.