Facet‐Induced Electron‐Bridge Enables Enhanced LiO 2 ‐Mediated Reaction Kinetics for Stable Lithium‐Oxygen Batteries

ABSTRACT Lithium oxygen batteries hold great promise as high‐energy‐density storage technologies, yet their practical implementation is hindered by sluggish cathode redox kinetics. A key bottleneck lies in the inefficient electron transfer associated with the formation and decomposition of the LiO 2 intermediate, which leads to severe polarization and rapid capacity fade. Herein, we propose a facet‐induced electron‐bridge engineering to boost LiO 2 ‐mediated reaction kinetics. By harnessing a Mott–Schottky built‐in electric field across the heterointerface, we drive directional charge separation that simultaneously tailors electron density and sorption microenvironments. The resulting intermediate‐binding energetics reprogram the reaction trajectory, affording precise manipulation over Li 2 O 2 nucleation kinetics and the subsequent pathways governing its growth and decomposition. Consequently, the engineered cathode thus delivers extended cycle life with a substantially reduced overpotential. This work provides a general principle for regulating reaction intermediates and accelerating electron transfer via crystal plane optimization and interfacial engineering, offering a reliable strategy for high‐performance electrocatalysts.