Stacking-Fault Enhanced Oxygen Redox in Li2MnO3

Lattice oxygen redox yields anomalous capacity and can significantly increase the energy density of layered Li-rich transition metal oxide cathodes, garnering tremendous interest. However, the mechanism behind O redox in these cathode materials is still under debate, in part due to the challenges in directly observing O and following associated changes upon electrochemical cycling. Here, with O-17 NMR as a direct probe of O activities, it is demonstrated that stacking faults enhance O redox participation compared with Li2MnO3 domains without stacking faults. This work is concluded by combining both ex situ and in situ O-17 NMR to investigate the evolution of O at 4i, 8j sites from monoclinic C2/m and 6c(1), 6c(2), 6c(3) sites from the stacking faults (P3(1)12). These measurements are further corroborated and explained by first-principles calculations finding a stabilization effect of stacking faults in delithiated Li2MnO3. In situ O-17 NMR tracks O activities with temporal resolution and provides a quantitative determination of reversible O redox versus irreversible processes that form short covalent O-O bonds. This work provides valuable insights into the O redox reactions in Li-excess layered cathodes, which may inspire new material design for cathodes with high specific capacity.