LAUSR

Rechargeable zinc–air batteries afford great potential toward next‐generation sustainable energy storage. Nevertheless, the oxygen redox reactions at the air cathode are highly sluggish in kinetics to induce poor energy efficiency and limited cycling lifespan. Air cathodes with asymmetric configurations significantly promote the electrocatalytic efficiency of the loaded electrocatalysts, whereas rational synthetic methodology to effectively fabricate asymmetric air cathodes remains insufficient. Herein, a strategy of asymmetric interface preconstruction is proposed to fabricate asymmetric air cathodes for high‐performance rechargeable zinc–air batteries. Concretely, the asymmetric interface is preconstructed by introducing immiscible organic–water diphases within the air cathode, at which the electrocatalysts are in situ formed to achieve an asymmetric configuration. The as‐fabricated asymmetric air cathodes realize high working rates of 50 mA cm−2, long cycling stability of 3400 cycles at 10 mA cm−2, and over 100 cycles under harsh conditions of 25 mA cm−2 and 25 mAh cm−2. Moreover, the asymmetric interface preconstruction strategy is universal to many electrocatalytic systems and can be easily scaled up. This work provides an effective strategy toward advanced asymmetric air cathodes with high electrocatalytic efficiency and significantly promotes the performance of rechargeable zinc–air batteries.