Optimising Ion Conductivity in NdBaInO₄-Based Phases

Abstract

Based on the previous work conducted by Fujii et al., NdBaInO4 compounds present modest oxide-ion conductivities. Therefore, it has been an attractive system of significant interest. In this study, we attempted to partially substitute Ca for Nd and the total electrical conductivity was successfully improved due to the generation of oxygen vacancies. The synthesis, crystal structure, density, surface topography, and electrical properties of NdBaInO4 and Ca-doped NdBaInO4 have been studied, respectively. NdBaInO4 and 10% and 20% molar fractions of Ca-doped NdBaInO4 were synthesized through solid-state reactions. The crystal structure of them was obtained from Le Bail refinement of the XRD pattern, giving the result of the monoclinic structure, which belongs to P21/c space group. The highest total electrical conductivity of 4.91 × 10−3 S cm−1 was obtained in the Nd0.9Ca0.1BaInO3.95 sample at a temperature of 760 °C in the dry atmosphere and the activation energy was reduced from 0.68 eV to 0.58 eV when the temperature was above 464 °C (737 K) after doping the NdBaInO4 with a 0.1 molar fraction of Ca2+. Moreover, the total conductivity of Nd0.9Ca0.1BaInO3.95 in the wet atmosphere at moderate temperature was relatively higher than that in the dry atmosphere, which suggests that potential proton conduction may exist in wet atmospheres. In addition, the oxygen diffusion coefficients of Nd0.9Ca0.1BaInO3.95 (D* = 1.82 × 10−8 cm2/s, 850 °C) was about two times higher than that of Nd0.8Ca0.2BaInO3.90 (D* = 7.95 × 10−9 cm2/s, 850 °C) and was increased significantly by two orders of magnitude when compared with the oxygen diffusion coefficient of the undoped NdBaInO4 (D* = 8.25 × 10−11 cm2/s, 850 °C).

Keywords

• Ca-doped NdBaInO₄
• oxide-ion conductivities
• electrical conductivity
• activation energy
• proton conduction
• oxygen diffusion coefficients