Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials

Li- and Mn-rich layered oxides are among the most promising cathode materials for Li-ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near-edge structure (FDMNES) code was combined with in situ X-ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition metals (TMs) in fresh and heavily cycled electrodes. Theoretical modeling reveals a recurring partially reversible LiMn₂ O₄ -like sub-nanodomain formation/dissolution process during each charge/discharge, which accumulates gradually and accounts for the Mn phase transition. From the modeling of spectra and maps of the valence state over large regions of the cathodes, it was found that the phase change is size-dependent. After prolonged cycling, the TMs displayed different levels of inactivity.