Recently, apatite-type phases, e.g., La10-x(Si/Ge)6O26+y, were attracting significant interest due to their high oxide ion conduction. Studies of the Ge-based systems have, however, shown them to suffer from problems related to Ge loss at the high sintering temperatures required to obtain dense pellets. In addition, the activation energy for oxide ion conduction was significantly higher in these systems than for the Si-based analogues. A detailed study was made of the mixed Si/Ge systems, La9.33Si6-xGexO26 in order to examine how these factors varied with Si/Ge ratio, and so determine the optimum Si/Ge ratio for high oxide ion conductivity. The results showed that the activation energy for oxide ion conduction increased with increasing Ge content, with evidence for an intermediate plateau for the range, x = 2 to 4. Conductivities lower than those previously reported were found for the Ge-based end-member (x = 6). Instead, the highest conductivity at 800C (0.06S/cm) was observed for intermediate compositions, x = 4. The results of extended sintering studies suggested that problems due to Ge loss increase with increasing Ge content, with extended heating at high temperatures ultimately leading to the formation of insulating La2GeO5 impurities, resulting in a significant decrease in the conductivity.

Oxide Ion Conductivity in the Mixed Si/Ge Apatite-Type Phases La9.33Si6-xGexO26. J.E.H.Sansom, P.R.Slater: Solid State Ionics, 2004, 167[1-2], 23-7