Enhanced acceptor concentration, proton conductivity, and hydration in multicomponent rare‐earth ortho‐niobates

Abstract

AbstractThe structural properties of (La0.2Nd0.2Sm0.2Gd0.2Eu0.2)1−xCaxNbO4−δ (x = 0–0.05) series have been studied by X‐ray powder diffraction at room temperature. The thermal properties were investigated using thermogravimetry, from which the concentration of proton defects was determined. Additionally, dilatometry studies were carried out, from which the thermal expansion coefficients and the phase transition temperature between low‐ and high‐temperature polymorphs were determined. In order to determine the electrical properties, the electrochemical impedance spectroscopy measurements under atmospheres of dry synthetic air and saturated with water vapor and heavy water at 300–800°C temperature range were performed. All the studied materials were single‐phase compositions and were stable in monoclinic I2/c crystal structure at room temperature. The water uptake studies revealed a small mass change under the switch from dry to humidified synthetic air atmospheres, suggesting the formation of proton defects. The phase transition from monoclinic to tetragonal crystal structure in the (La0.2Nd0.2Sm0.2Gd0.2Eu0.2)1−xCaxNbO4−δ (x = 0–0.05) series occurs above 650°C. A small amount of calcium dopant increases the total conductivity in all tested atmospheres by two orders of magnitude, for example, from 0.34 μS cm−1 in La0.2Nd0.2Sm0.2Gd0.2Eu0.2NbO4 to 63.7 μS cm−1 in (La0.2Nd0.2Sm0.2Gd0.2Eu0.2)0.95Ca0.05NbO4−δ at 700°C in humid synthetic air atmosphere.