Enhanced reversible capacity and cycling stability of Li_1.2Ni_0.13Fe_0.13Mn_0.54O₂ via Mo-doped induced low Li/Ni site disorder

Li-ion batteries(LIBs) are widely used in mobile devices and electric vehicles, but the traditional layered transition metal cathode material, LiTMO₂(TM=Ni, Co, Mn, or Al), has a low energy density that cannot satisfy the demand of commercial applications, and Li-rich Mn-based layered oxides(LRLOs) are a strong competitor to the traditional layered cathode materials for their specific capacity of more than 200 mAh/g. Due to the high energy density and low cost, Li-rich Mn-based layered oxides(LRLO) have been a promising candidate cathode for next-generation Li-ion batteries. The anionic redox reaction(ARR) in LRLO destabilizes the lattice oxygen, leading to voltage degradation and capacity loss. Although iron-substituted cobalt-free Li-rich materials can achieve less voltage decay, they suffer from severe cation disorder and poor kinetics. Here, we developed a simple and feasible high-valent ion doping strategy by doping Mo into Li_1.2Ni_0.13Fe_0.13Mn_0.54O₂(LNFMO), which expands the Li layer spacing, provides a broader channel for Li⁺ transport, improves the diffusion kinetics of Li⁺, effectively suppresses the cation disorder, and further stabilizes the layered structure. As a result, the Mo-doped LRLO exhibited significantly enhanced electrochemical performance, with an initial reversible capacity of 209.48 mAh/g at 0.2 C, and the initial specific capacity increased from 137.02 mAh/g to 165.15 mAh/g at 1 C. After 300 cycles, there is still a specific capacity of 117.49 mAh/g for the Mo-doped cathode, and the voltage decay is reduced from 2.09 mV/cycle to 1.66 mV/cycle. The Mo-doped LRLO are systematically characterized, and the mechanism of cycle stabilization is revealed, which provides an important reference for designing high performance Li-rich cathode.