Origin of the low grain boundary conductivity in lithium ion conducting perovskites: Li3xLa0.67-xTiO3.

Although the bulk conductivity of lithium ion conducting Li3xLa0.67-xTiO3 electrolytes reaches the level of 10-3 S cm-1, the grain boundary conductivity is orders of magnitude lower; the origin of the low grain boundary conductivity should be thoroughly understood as a prerequisite to improve the overall conductivity. Samples with grain sizes ranging from 25 nm to 3.11 μm were prepared. According to SEM and TEM investigations, the grain boundaries are free of any second phase; however, the grain boundary conductivity is still ∼4 orders of magnitude lower than the bulk conductivity. The grain boundary conductivity decreases with decreasing grain size, indicating that the low grain boundary conductivity is not dominated only by the crystallographic grain boundary. Since electrons are attracted to the grain boundaries, as reflected by the dramatically enhanced grain boundary conductivity when electrons are introduced, the grain boundary core in Li3xLa0.67-xTiO3 should be positively charged, causing the depletion of lithium ions in the adjacent space-charge layers. The very low grain boundary conductivity can be accounted for by the lithium ion depletion in the space-charge layer.