Regulating the Potential of Anion Redox to Reduce the Voltage Hysteresis of Li-Rich Cathode Materials

Layered Li-rich oxides (LROs) that exhibit anionic and cationic redox are extensively studied due to their high energy storage capacities. However, voltage hysteresis, which reduces the energy conversion efficiency of the battery, is a critical limitation in the commercial application of LROs. Herein, using two Li₂RuO₃ (LRO) model materials with C2/c and P2₁/m symmetries, we explored the relationship between voltage hysteresis and the electronic structure of Li₂RuO₃ by neutron diffraction, in situ X-ray powder diffraction, X-ray absorption spectroscopy, macro magnetic study, and electron paramagnetic resonance (EPR) spectroscopy. The charge-transfer band gap of the LRO cathode material with isolated eg electron filling decreases, reducing the oxidation potential of anion redox and thus displaying a reduced voltage hysteresis. We further synthesized Mn-based Li-rich cathode materials with practical significance and different electron spin states. Low-spin Li1.15Ni0.377Mn0.473O₂ with isolated eg electron filling exhibited a reduced voltage hysteresis and high energy conversion efficiency. We rationalized this finding via density functional theory calculations. This discovery should provide critical guidance in designing and preparing high-energy layered Li-rich cathode materials for use in next-generation high-energy-density Li-ion batteries based on anion redox activity.