DFT Electronic Properties and Synthesis Thermodynamics of Li_xLa_1-xTiO₃Electrolytes for Li-Ion Batteries

Lithium lanthanum titanate perovskites Li x La1-x TiO3 (LLTO) are promising solid-electrolytes for Li-ion batteries. We studied, in the Density-Functional-Theory framework, the thermodynamic stability and the electronic and magnetic properties of LLTO, as bulk materials and as thin slabs with (001) exposed surfaces. Results show that LaTiO3 (LTO) exhibits semiconductor behavior and G-type antiferromagnetic order (AFMG), whereas the TiO2-terminated LTO slab is a semiconductor with ferromagnetic (FM) order. Contrasting, the LTO slab exposing a LaO-terminated surface is a conductor with AFMG ordered Ti cations' magnetic moments (MMs), but at the surface there are some FM ordered MMs (La atoms). LLTO bulk electrolyte is a semiconductor (x = 0.25) or insulator (x = 0.50). The LLTO slab is a FM (non-magnetic) conductor (TiO2 (LiO)-terminated surface) or a FM semiconductor (LaO-terminated). Besides, the stability of the LLTO bulk and slabs structures was analyzed, as well as the slabs' preferences for LiO, LaO or TiO2 ends.