Electrophysical characteristics and stability of solid apatite-like electrolytes La x Si6O12 + 1.5x and La x Ge6O12 + 1.5x

Abstract

Oxygen-ion conduction in apatite-like compounds based on silicates and germanates of lanthanum La x A6O12 + 1.5x (A = Si, Ge; x = 9.11–10.22) is studied. The compounds are shown to be purely ionic conductors at 600–900°C and partial oxygen pressures 10−16 to 105 Pa. The electroconductivity of the best conducting specimens of La x A6O12 + 1.5x (A = Si, Ge; x = 9.77–10) exceeds that of electrolyte YSZ at moderate temperatures. The electroconductivity of lanthanum germanate is substantially greater than that of lanthanum silicate, specifically, 7.85 × 10−2 and 2.35 × 10−2 S cm−1, respectively, at 800°C. An inflection is discovered at ∼750°C in the temperature dependences of electroconductivity of La x Ge6O12 + 1.5x (x = 9.77–10.22). A dilatometric examination points to a second-kind phase transition that may be due to the oxygen sublattice disordering. The behavior of apatite-like electrolytes La x A6O12 + 1.5x (A = Si, Ge) during long exploitation periods in the interval of working temperatures of electrochemical devices is studied for the first time ever. The electrolytes’ aging at 800°C in air for 1000 h was investigated by the electroconductivity method. The electroconductivity of lanthanum germanates decayed with time by 5% and that of lanthanum silicates, by 9.5%. The steady-state values of electroconductivity of all compounds studied is reached after 600–700 h. The compounds studied form a class of materials that hold some promise as solid electrolytes for medium-temperature fuel cells and other electrochemical devices.