Unusual Spinel-to-Layered Transformation in LiMn 2 O 4 Cathode Explained by Electrochemical and Thermal Stability Investigation.

Distorted surface regions (5-6 nm) with an unusual layered-like structure on LiMn2 O4 cathode material were directly observed after it was cycled (3-4.9 V), indicating a possible spinel-to-layered structural transformation. Formation of these distorted regions severely degrades LiMn2 O4 cathode capacity. As we attempt to get a better understanding of the exact crystal structure of the distorted regions, the structural transformation pathways and the origins of the distortion are made difficult by the regions' nanoscopic size. Inspired by the reduction of Mn4+ to Mn3+ in surface electronic structures that might be associated with oxygen loss during cycling, we further investigated the atomic-level surface structure of LiMn2 O4 by heat-treatments between 600 and 900 °C in various atmospheres, finding similar surface spinel-to-layered structural transformation only for LiMn2 O4 heat-treated in argon atmosphere for a few minutes (or more). Controllable and measurable oxygen loss during heat-treatments result in Mn3+ for charge compensation. The ions then undergo a disproportionation reaction, driving the spinel-to-layered transformation by way of an intermediate LiMn3 O4 -like structure. The distortion of the surface regions can be extended to the whole bulk by heat-treatment for 300-600 min, ultimately enabling us to identify the bulk-level structure as layered Li2 MnO3 (C2/m). This work demonstrates the critical role of Mn3+ in controlling the kinetics of the structural transformation in spinel LiMn2 O4 and suggests heat-treatment in argon as a convenient method to control the surface oxygen loss and consequently reconstruct the atomic-level surface structure.