This work continues our systematic study of Li- and Mn- rich cathodes for lithium-ion batteries. We chose Li2MnO3 as a model electrode material with the aim of correlating the improved electrochemical characteristics of these cathodes initially activated at 0 °C with the structural evolution of Li2MnO3, oxygen loss, formation of per-oxo like species (O22−) and the surface chemistry. It was established that performing a few initial charge/discharge (activation) cycles of Li2MnO3 at 0 °C resulted in increased discharge capacity and higher capacity retention, and decreased and substantially stabilized the voltage hysteresis upon subsequent cycling at 30 °C or at 45 °C. In contrast to the activation of Li2MnO3 at these higher temperatures, Li2MnO3 underwent step-by-step activation at 0 °C, providing a stepwise traversing of the voltage plateau at >4.5 V during initial cycling. Importantly, these findings agree well with our previous studies on the activation at 0 °C of 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2 materials. The stability of the interface developed at 0 °C can be ascribed to the reduced interactions of the per-oxo-like species formed and the oxygen released from Li2MnO3 with solvents in ethylene carbonate–methyl-ethyl carbonate/LiPF6 solutions. Our TEM studies revealed that typically, upon initial cycling both at 0 °C and 30 °C, Li2MnO3 underwent partial structural layered-to-spinel (Li2Mn2O4) transition.
