Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

The first-cycle behavior of layered Li-rich oxides, including Li2MnO3 activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li2MnO3 activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi2MnO3·(1–x) LiNi0.3Co0.3Mn0.4O2 (x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li2MnO3 and LiNi0.3Co0.3Mn0.4O2 structures can significantly affect the activation pathway of Li1.2Ni0.12Co0.12Mn0.56O2, leading to an extra-high capacity. It is demonstrated that Li2MnO3 activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li2MnO3 governed by chemical decomposition (Li2O evolution). CEI evolution is closely related to Li+ extraction/insertion. The valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.