A ΔE = 0.63 V Bifunctional Oxygen Electrocatalyst Enables High‐Rate and Long‐Cycling Zinc–Air Batteries

Abstract Rechargeable zinc–air batteries constitute promising next‐generation energy storage devices due to their intrinsic safety, low cost, and feasibility to realize high cycling current density and long cycling lifespan. Nevertheless, their cathodic reactions involving oxygen reduction and oxygen evolution are highly sluggish in kinetics, requiring high‐performance noble‐metal‐free bifunctional electrocatalysts that exceed the current noble‐metal‐based benchmarks. Herein, a noble‐metal‐free bifunctional electrocatalyst is fabricated, which demonstrates ultrahigh bifunctional activity and renders excellent performance in rechargeable zinc–air batteries. Concretely, atomic Co–N–C and NiFe layered double hydroxides (LDHs) are respectively selected as oxygen reduction and evolution active sites and are further rationally integrated to afford the resultant CoNC@LDH composite electrocatalyst. The CoNC@LDH electrocatalyst exhibits remarkable bifunctional activity delivering an indicator Δ E of 0.63 V, far exceeding the noble‐metal‐based Pt/C + Ir/C benchmark ( Δ E = 0.77 V) and most reported electrocatalysts. Correspondingly, ultralong lifespan (over 3600 cycles at 10 mA cm −2 ) and excellent rate performances (cycling current density at 100 mA cm −2 ) are achieved in rechargeable zinc–air batteries. This work highlights the current advances of bifunctional oxygen electrocatalysis and endows high‐rate and long‐cycling rechargeable zinc–air batteries for efficient sustainable energy storage.