Ca, Sr or Mg-doped Ceria Electrolytes Prepared by Citrate-Nitrate Combustion Synthesis: Effect of Doping Concentration

Journal of Electroceramics Pub Date: 2023-03-16 DOI: 10.1007/s10832-023-00306-0

Abstract
In this work, it was aimed to synthesize and characterize rare earth metal-free cerium-based electrolytes that might be used in solid oxide fuel cells (SOFCs) by doping calcium, strontium, or magnesium to CeO2. For this purpose, CeO2, CaxCe(1-x)O(2?δ) (0.16 ≤ x ≤ 0.24), SrxCe(1-x)O(2?δ) (0.02 ≤ x ≤ 0.08) and MgxCe(1-x)O(2?δ) (0.07 ≤ x ≤ 0.13) were prepared by using citrate-nitrate combustion method. The solubility limits, microstructural and physical properties of the samples were characterized with XRD, SEM, TG-DTA and impedance analysis. It was found that all samples were in fluorite structure similar to the undoped ceria. The solubility limits of Ca2+, Sr2+ and Mg2+ were 21%, 6% and 12% (by mole) respectively based on XRD analysis results. The relative densities of sintered pellets at 1400 °C were more than 90%. Electrochemical impedance spectroscopy analysis, in which the ionic conductivities of the samples were measured, revealed that the Ca0.2Ce0.8O2-δ (CCO20) sample sintered at 1400 °C showed the highest ionic conductivity value of 4.47 x10-2 S.cm?1 at 800 °C. It was determined that the O2- ion conductivity decreased with the order of Ca2+ ≈ Sr2+ >> Mg2+. Conductivities increased with increasing dopant ratio, reached a maximum below the ratios of solubility limits, and then decreased. The obtained results showed that Ca or Sr doped electrolytes prepared by the citrate-nitrate method can show ionic conductivities close to the state-of-the-art Sm doped Ceria electrolytes. It has been determined that Mg doping is quite ineffective.
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