Quantitative Delineation of the Low Energy Decomposition Pathway for Lithium Peroxide in Lithium–Oxygen Battery

Identification of a low‐potential decomposition pathway for lithium peroxide (Li(2)O(2)) in nonaqueous lithium–oxygen (Li–O(2)) battery is urgently needed to ameliorate its poor energy efficiency. In this study, experimental data and theoretical calculations demonstrate that the recharge overpotential (η (RC)) of Li–O(2) battery is fundamentally dependent on the Li(2)O(2) crystallization pathway which is intrinsically related to the microscopic structural properties of the growing crystals during discharge. The Li(2)O(2) grown by concurrent surface reduction and chemical disproportionation seems to form two discrete phases that have been deconvoluted and the amount of Li(2)O(2) deposited by these two routes is quantitatively estimated. Systematic analyses have demonstrated that, regardless of the bulk morphology, solution‐grown Li(2)O(2) shows higher η (RC) (>1 V) which can be attributed to higher structural order in the crystal compared to the surface‐grown Li(2)O(2). Presumably due to a cohesive interaction between the electrode surface and growing crystals, the surface‐grown Li(2)O(2) seems to possess microscopic structural disorder that facilitates a delithiation induced partial solution‐phase oxidation at lower η (RC) (<0.5 V). This difference in η (RC) for differently grown Li(2)O(2) provides crucial insights into necessary control over Li(2)O(2) crystallization pathways to improve the energy efficiency of a Li–O(2) battery.