Determining Factors in Triggering Hysteretic Oxygen Capacities in Lithium-Excess Sodium Layered Oxides.

Oxygen redox (OR) reactions in sodium layered oxide cathodes have been studied intensively to harness their full potential in achieving high energy density for sodium-ion batteries (SIBs). However, OR triggers a large hysteretic voltage during discharge after the first charge process for OR-based oxides, and its intrinsic origin is unclear. Therefore, in this study, an in-depth reinvestigation on the fundamentals of the reaction mechanism in Na[LiMn]O with a Mn/Li ratio () of 2 was performed to determine the factors that polarize the OR activity and to provide design rules leading to nonhysteretic oxygen capacity using first-principles calculations.