Oxygen Vacancy Diffusion and Condensation in Lithium‐Ion Battery Cathode Materials

Abstract Oxygen vacancies (OV) are native defects in transition metal (TM) oxides and their presence has a critical effect on the physicochemical properties of the oxide. Metal oxides are commonly used in lithium‐ion battery (LIB) cathodes and there is still a lack of understanding of the role of OVs in LIB research field. Here, we report on the behavior of OVs in a single‐crystal LIB cathode during the non‐equilibrium states of charge and discharge. We found that microcrack evolution in a single crystal occurs due to OV condensation in specific crystallographic orientations generated by the continuous migration of OVs and TM ions. Moreover, understanding the effects of the presence and diffusion of OVs in metal oxides enables the elucidation of most of the conventional mechanisms of capacity fading in LIBs and provides new insights for new electrochemical applications.