Structural insights into composition design of Li-rich layered cathode materials for high-energy rechargeable battery

The Li-rich layered oxide is considered as one of the most promising cathode materials for high energy density batteries, due to its ultrahigh capacity derived from oxygen redox. Although incorporating over-stoichiometric Li into layered structure can generate Li₂MnO₃-like domain and enhance the oxygen redox activity thermodynamically, the fast and complete activation of the Li₂MnO₃-like domain remains challenging. Herein, we performed a systematic study on structural characteristics of Li-rich cathode materials to decipher the factors accounting for activation of oxygen redox. We reveal that the activation of Li-rich cathode materials is susceptible to local Co coordination environments. The Co ions can intrude into Li₂MnO₃-like domain and modulate the electronic structure, thereby facilitating the activation of Li-rich layered cathode materials upon first charging, leading to higher reversible capacity. In contrast, Li₂MnO₃-like domain hardly contains any Ni ions which contribute little to the activation process. The optimum composition design of this class of materials is discussed and we demonstrate a small amount of Co/Mn exchange in Li₂MnO₃-like domain can significantly promote the oxygen redox activation. Our findings highlight the vital role of Co ions in the activation of oxygen redox Li-rich layered cathode materials and provide new insights into the pathway toward achieving high-capacity Li-rich layered cathode materials.