Surface Evolution of Lithium Titanate upon Electrochemical Cycling Using a Combination of Surface Specific Characterization Techniques

Abstract Among the electrodes for Li‐ion batteries, Li₄Ti₅O₁₂ (LTO) stands out as anode owing to its stability and safety, in part ascribed to its low surface reactivity. However, the overlayer formation on the LTO surface upon electrochemical cycling is reported in recent years; a rough surface layer of electrochemically inactive α‐Li₂TiO₃ on top of the LTO (111) surface is suggested on the grounds of scanning probe techniques and theoretical ab initio calculations which would negatively strike on the battery performance. Hence the investigation of the LTO surface evolution is key to achieve more stable and safer Li‐ion batteries. LTO (111) thin film electrodes are used as model system where a variety of surface specific characterization techniques are applied to unveil the surface behavior of LTO in Li‐ion batteries. In contrast with previous studies, with the help of high‐resolution transmission electron microscopy and synchrotron‐based surface X‐ray diffraction, α‐Li₂TiO₃ is found to be a surface preparation product. Of special importance is the use of high‐resolution electron backscatter diffraction to report an increase on the LTO surface strain upon electrochemical cycling which can have a critical effect in long cycling performance of LTO that is always considered a zero‐strain material.