Oxygen-ion diffusion and electrical conductionof LaMoFeO systems

Based on the novel oxygen ion conductor La₂Mo₂O₉, a series of Fe-doped samples of La₂Mo_2-xFe_xO_9-? (x = 0, 0.025, 0.05, 0.1) was prepared by conventional solid-state reaction method. The structure, phase transition, oxygen ion diffusion and electrical conductivity were studied with X-ray diffraction (XRD), differential scanning calorimeter (DSC), direct current (dc) resistivity, and dielectric relaxation (DR) measurements. One DR peak associated with the short-distance diffusion of oxygen vacancies was observed in both temperature and frequency spectra. The activation energy for oxygen ion diffusion in Fe-doped La₂Mo₂O₉ samples was smaller than that in un-doped samples. Fe doping can increase the ionic conductivity of La₂Mo_2-xFe_xO_9-? samples as well as the ionic transference number in the temperature range from 680°C to 400°C in comparison with the un-doped samples, although the electronic conductivity slightly increases. It is found that because of the small solubility of Fe₂O₃ in La₂Mo₂O₉ (<5%), Fe doping cannot suppress the phase transition that occurred around 570°C, but 2.5% K doping at La site at the same time (e.g. in sample La_1.95K_0.05Mo_1.95Fe_0.05O_9-?) can completely suppress this phase transition and increase conductivity at lower temperatures.