LAUSR

Since the recognition of a significant oxygen-redox contribution to enhancing the capacity of Li transition-metal oxide cathodes, the oxygen release and subsequent structural variations together with capacity fading have been critical issues to achieve better electrochemical performance. As most previous reports dealt with the structural degradation of cathodes after electrochemical cycling, it has been fairly difficult to clarify how substantial the effect of lattice strain on the oxygen release would be while exclusively ruling out any electrochemical influences. By utilizing nanoindentation and mechanical surface polishing of single-crystal LiCoO2 and Li2 MnO3 , we scrutinize the local variations of both the atomic structure and oxygen content. Atomic-column-resolved imaging reveals that local Li-M (M = Co and Mn) disordering and further amorphization are induced by mechanical strain. Moreover, substantial oxygen deficiency in the regions with these structure changes is directly identified by spectroscopic analyses. Ab initio density functional theory calculations also demonstrate energetically favorable formation of oxygen vacancies under shear strain. Providing direct evidence of oxygen release as a consequence of lattice strain, the findings in this work suggest that efficient strain relaxation will be of great significance for longevity of the anion framework in layered oxide cathodes. This article is protected by copyright. All rights reserved.