A Gradient Doping Strategy toward Superior Electrochemical Performance for Li‐Rich Mn‐Based Cathode Materials

Lithium-rich layered oxides (LLOs) are concerned as promising cathode materials for next-generation lithium-ion batteries due to their high reversible capacities (larger than 250 mA h g^-1 ). However, LLOs suffer from critical drawbacks, such as irreversible oxygen release, structural degradation, and poor reaction kinetics, which hinder their commercialization. Herein, the local electronic structure is tuned to improve the capacity energy density retention and rate performance of LLOs via gradient Ta⁵⁺ doping. As a result, the capacity retention elevates from 73% to above 93%, and the energy density rises from 65% to above 87% for LLO with modification at 1 C after 200 cycles. Besides, the discharge capacity for the Ta⁵⁺ doped LLO at 5 C is 155 mA h g^-1 , while it is only 122 mA h g^-1 for bare LLO. Theoretical calculations reveal that Ta⁵⁺ doping can effectively increase oxygen vacancy formation energy, thus guaranteeing the structure stability during the electrochemical process, and the density of states results indicate that the electronic conductivity of the LLOs can be boosted significantly at the same time. This strategy of gradient doping provides a new avenue to improve the electrochemical performance of the LLOs by modulating the local structure at the surface.