In situ small-angle X-ray scattering reveals solution phase discharge of Li-O₂ batteries with weakly solvating...

Electrodepositing insulating lithium peroxide (Li₂O₂) is the key process during discharge of aprotic Li-O₂ batteries and determines rate, capacity, and reversibility. Current understanding states that the partition between surface adsorbed and dissolved lithium superoxide governs whether Li₂O₂ grows as a conformal surface film or larger particles, leading to low or high capacities, respectively. However, better understanding governing factors for Li₂O₂ packing density and capacity requires structural sensitive in situ metrologies. Here, we establish in situ small- and wide-angle X-ray scattering (SAXS/WAXS) as a suitable method to record the Li₂O₂ phase evolution with atomic to submicrometer resolution during cycling a custom-built in situ Li-O₂ cell. Combined with sophisticated data analysis, SAXS allows retrieving rich quantitative structural information from complex multiphase systems. Surprisingly, we find that features are absent that would point at a Li₂O₂ surface film formed via two consecutive electron transfers, even in poorly solvating electrolytes thought to be prototypical for surface growth. All scattering data can be modeled by stacks of thin Li₂O₂ platelets potentially forming large toroidal particles. Li₂O₂ solution growth is further justified by rotating ring-disk electrode measurements and electron microscopy. Higher discharge overpotentials lead to smaller Li₂O₂ particles, but there is no transition to an electronically passivating, conformal Li₂O₂ coating. Hence, mass transport of reactive species rather than electronic transport through a Li₂O₂ film limits the discharge capacity. Provided that species mobilities and carbon surface areas are high, this allows for high discharge capacities even in weakly solvating electrolytes. The currently accepted Li-O₂ reaction mechanism ought to be reconsidered.