Abstract
Lithium ion-conducting perovskite-type oxides, e.g. La2/3-xLi3xTiO3 show high ionic conductivities as high as 10-5-10-3 Scm-1 at room temperature. Their high conductivities are attributed to the percolation-controlled diffusion of lithium ions via vacancies in the A-site-deficient perovskites (general formula of perovskite-type oxide: ABO3). The strong correlation between structure and percolation-controlled diffusion in the perovskites is primarily referred to the arrangement of A-site ions, and the "bottleneck" square-surrounded by four oxygen ions. The bottleneck size, i.e., the repulsion for lithium ions by the electronic clouds of oxygen ions, is dependent on the distortion and tilt of BO6 octahedra, which relate to the difference of skeletal ions, A and B cations, i.e., tolerance factor and their chemical characters, and is the predominant factor of the activation energy for ion migration. The ionic conduction in lithium ion-conducting perovskites is discussed in the view of crystal chemistry.