Insight into the synthesis and electrical properties of alkali-earth-substituted Gd3GaO6 oxide-ion and proton conductors

• Discovery of new oxide-ion and proton conductors by cation substitutions in Gd3GaO6.
• The role of the substituents on the sintering and transport properties is emphasized.
• Insight into electrical properties is carried on by varying relevant parameters.
• The best material exhibits electrical properties comparable to that of doped LaNbO4.

Novel ionic conductors were prepared by substituting Ca2+ and Sr2+ for Gd3+ in Gd3GaO6. A microwave-assisted combustion technique was used to synthesize these compounds at 900 °C. SEM observations showed that both substituents promote grain growth during sintering. XRD proved that the Gd3-x(Ca,Sr)xGaO6-x/2 solid solutions are formed up to x = 0.10. Below 600 °C, the level of conductivity under wet Ar is higher than that of measured under dry atmospheres, thereby demonstrating the contribution of proton defects to the overall conductivity. The highest level of proton conduction, i.e. σ600°C = 1 × 10−3 S cm−1, was measured for Gd2.9Sr0.1GaO5.95 at 600 °C in wet Ar. At higher temperatures, only oxygen ions contribute to the conductivity. At 800 °C, a total oxide-ion conductivity of σ800°C = 1 × 10−2 S cm−1 was measured for the highest substitution level, i.e. x = 0.10. In both temperature ranges, activation energy associated with ionic transport decreases with the Me content as a result of an increase in grain size. Stability tests were successfully achieved as the structure of materials remains unchanged after different treatment under severe conditions. Conductivity measurements under varying oxygen partial pressures demonstrated that materials are purely oxide-ion conductors up to pO2 = 1 × 10−5 atm. At higher pO2, a p-type contribution appears.