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

Abstract

AbstractLi‐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.