Excess-Li Localization Triggers Chemical Irreversibility in Li- and Mn-Rich Layered Oxides

Li- and Mn-rich layered oxides (LMRs) have emerged as practically feasible cathode materials for high-energy-density Li-ion batteries due to their extra anionic redox behavior and market competitiveness. However, sluggish kinetics regions (<3.5 V vs Li/Li⁺) associated with anionic redox chemistry engender LMRs with chemical irreversibility (first-cycle irreversibility, poor rate properties, voltage fading), which limits their practical use. Herein, the structural origin of this chemical irreversibility is revealed through a comparative study involving Li_1.15Mn_0.51Co_0.17Ni_0.17O₂ with relatively localized and delocalized excess-Li in its lattice system. Operando fine-interval X-ray absorption spectroscopy is used to simultaneously observe the interplay between transition-metal–oxygen (TM-O) redox chemistry and TM migration behavior in real time. Density functional theory calculations show that excess-Li localization in the LMR structure attenuates TM-O covalency and stability, leading to overall chemical irreversibility. Hence, the delocalized excess-Li system is proposed as an alternative design for practically feasible LMR cathodes with restrained TM migration and sustainable O-redox chemistry.