Influence of anionic vacancies on the conductivity of La9.33Si6−xAlxO26−x/2 oxide conductors with an oxyapatite structure

Al-doped oxyapatite-type lanthanum silicates La9.33Si6−xAlxO26−x/2□x/2 (x = 0, 0.4, 0.8 and 1) powders have been prepared by the solid state reaction at high temperature in order to determine the influence of anionic vacancies on the electrical properties of the material. The crystal structure and properties of La9.33Si6−xAlxO26−x/2□x/2 powders have been studied by X-ray diffraction (XRD) patterns, magic-angle spinning nuclear magnetic resonance (MAS-NMR) technique and complex impedance analysis. All the compounds of La9.33Si6−xAlxO26−x/2□x/2 oxyapatites doped with Al3+ consist of a hexagonal structure with a P63/m space group. Lanthanum silicates doped with trivalent Al3+ have a higher conductivity than those without trivalent Al3+ at the Si4+ site. The extra oxygen O(4) atoms in site 2a (0, 0, 0.25) occupy channels running through the structure that are responsible for the high oxygen ion conduction. However, Al substitution seems to produce oxygen vacancies and create another pathway for oxide ions. The expansion of the channels (La(1)-O(4) distance) leads to an increase in the conductivity. For the best sample (x = 1), the conductivity observed was 5 × 10−3 S cm−1 at 750 °C.