Jointly Improving Anionic–Cationic Redox Reversibility of Lithium-Rich Manganese-Based Cathode Materials by N Surface Doping

The lithium-rich manganese-based layer oxide (LRMO) with high specific capacity (∼300 mAh g^-1) and economic feasibility is accepted as the cathode material for high energy density rechargeable batteries. Accompanied by the additional anionic redox reactions during the initial charging process, LRMO presents oxygen release, sluggish Li⁺ diffusion, and irreversible transition metal ion (TM) migration, which is responsible for its severe structural deterioration and rapid capacity/voltage decay. Here, the N doping strategy is proposed via feasible treatment of oxygen-vacancy-containing Li_1.16Ni_0.21Mn_0.63O_2-δ (LNMO) particles. The as obtained LNMO-N samples demonstrate doping N, partially reduced Mn/Ni cations, and oxygen vacancies on the surface. The DFT calculations and experimental results demonstrate that N replacing the crystal oxygen sites on the surface reduces the energy barrier for diffusion, thereby enhancing the kinetics of Li⁺ diffusion and improving the reversibility of transition metal migration. Furthermore, N doping induces stacking faults and a more flexible structure. Therefore, LNMO-N exhibits a significantly improved anionic-cationic redox reaction reversibility with a high discharge specific capacity of 296.6 mAh g^-1 at 20 mA g^-1 within the range of 2.0 to 4.8 V and an impressive initial Coulombic efficiency of 85.9%. Moreover, the rate capability is obviously improved with a remarkable capacity of 215.1 mAh g^-1 at 200 mA g^-1 in 200 cycles with a capacity retention of 72.52% and exceptional performance of 141.4 mAh g^-1 even at a higher current density of 1000 mA g^-1.