Formation and stability of small polarons at the lithium-terminated Li₄Ti₅O₁₂ (LTO) (111) surface

Zero strain insertion, high cycling stability, and a stable charge/discharge plateau are promising properties rendering Lithium Titanium Oxide (LTO) a possible candidate for an anode material in solid state Li ion batteries. However, the use of pristine LTO in batteries is rather limited due to its electronically insulating nature. In contrast, reduced LTO shows an electronic conductivity several orders of magnitude higher. Studying bulk reduced LTO, we could show recently that the formation of polaronic states can play a major role in explaining this improved conductivity. In this work, we extend our study toward the lithium-terminated LTO (111) surface. We investigate the formation of polarons by applying Hubbard-corrected density functional theory. Analyzing their relative stabilities reveals that positions with Li ions close by have the highest stability among the different localization patterns.