Influence of isovalent ‘w’ substitutions on the structure and electrical properties of la₂mo₂o₉ electrolyte for intermediate-temperature solid oxide fuel cells

Lanthanum molybdenum oxide (La₂Mo₂O₉, LAMOX)-based ion conductors have been used as potential electrolytes for solid oxide fuel cells. The parent compound La₂Mo₂O₉ undergoes a structural phase transition from monoclinic (P2₁ ) to cubic (P2₁3) at 580^◦C, with an enhancement in oxide ion conductivity. The cubic phase is of interest because it is beneficial for oxide ion conduction. In search of alternative candidates with a similar structure that might have a stable cubic phase at lower temperatures, we have studied the variations of the crystal structure and ionic conductivity for 25, 50, 62.5 and 75 mol% W substitutions at the Mo site using high-temperature X-ray diffraction, dilatometry, and impedance spectroscopy. Highly dense ceramic samples have been synthesized by solid-state reaction in a two-step sintering process. Low-angle X-ray diffraction and Rietveld refinement confirm the stabilization of the cubic phase for all compounds in the entire temperature range considered. The substitutions of W at the Mo site produce a decrement in the lattice parameter. The thermal expansion coefficients in the high-temperature range of the W-substituted ceramics, as determined by dilatometry, are much higher than that of the unmodified sample. The impedance spectra have been modeled using a modified genetic algorithm within 300–600^◦C. A distribution function of the relaxation times is obtained, and the contributions of ohmic drop, grains and grain boundaries to the conductivity have been identified. Overall, our investigation provides information about cationic substitution and insights into the understanding of oxide ion conductivity in LAMOX-based compounds for developing solid oxide fuel cells.