Formulating Local Environment of Oxygen Mitigates Voltage Hysteresis in Li‐Rich Materials

Li-rich cathode materials have emerged as one of the most prospective options for Li-ion batteries owing to their remarkable energy density (>900 Wh kg⁻¹). However, voltage hysteresis during charge and discharge process lowers the energy conversion efficiency, which hinders their application in practical devices. Herein, the fundamental reason for voltage hysteresis through investigating the O redox behavior under different (de)lithiation states is unveiled and it is successfully addressed by formulating the local environment of O²⁻. In Li-rich Mn-based materials, it is confirmed that there exists reaction activity of oxygen ions at low discharge voltage (<3.6 V) in the presence of TM-TM-Li ordered arrangement, generating massive amount of voltage hysteresis and resulting in a decreased energy efficiency (80.95%). Moreover, in the case where Li 2b sites are numerously occupied by TM ions, the local environment of O²⁻ evolves, the reactivity of oxygen ions at low voltage is significantly inhibited, thus giving rise to the large energy conversion efficiency (89.07%). This study reveals the structure-activity relationship between the local environment around O²⁻ and voltage hysteresis, which provides guidance in designing next-generation high-performance cathode materials.