Local structure transformations promoting high lithium diffusion in defect perovskite type structures

Defect perovskites, AxBO3 such as (Li3xLa2/3-x)TiO3, are attracting attention as high capacity electrodes in lithium-ion batteries. However, the mechanism enabling high lithium storage capacities has not been fully investigated. In this work, the reversible insertion and removal of lithium up to an average A-site cavity occupancy of 1.71 in the defect perovskite (Li0.18Sr0.66)(Ti0.5Nb0.5)O3 is investigated. It was shown that subtle lithium reorganization during lithiation has a significant impact on enabling high capacity. Contrary to previous studies, lithium was coordinated to triangular faces of Ti/Nb oxygen octahedra and offset from O4 windows between A-site cavities in the as-synthesised material. Upon electrochemical lithiation Li-Li repulsion redistributes of all the lithium towards the O4 window position resulting in a loss of lithium mobility. Surprisingly, the mobility is regained during over-lithiation and following multiple electrochemical cycles. It is suggested that lithium reorganisation into the center of the O4 window alleviates the Li-Li repulsion and modifies the diffusion behavior from site percolation to bond percolation. The results obtained provide valuable insight into the chemical drivers enabling higher capacities and enhanced diffusion in defect perovskites. More broadly the study delivers fundamental understanding on the non-equilibrium structural transformations occurring within electrode materials during repeated electrochemical cycles. © 2022