A “Pre‐Division Metal Clusters” Strategy to Mediate Efficient Dual‐Active Sites ORR Catalyst for Ultralong Rechargeable Zn‐Air Battery

Abstract To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal‐air batteries, catalysts with dual‐active centers have stood out. Here, a “pre‐division metal clusters” strategy is firstly conceived to fabricate a N,S‐dual doped honeycomb‐like carbon matrix inlaid with CoN 4 sites and wrapped Co 2 P nanoclusters as dual‐active centers (Co 2 P/CoN 4 @NSC‐500). A crystalline {Co II 2 } coordination cluster divided by periphery second organic layers is well‐designed to realize delocalized dispersion before calcination. The optimal Co 2 P/CoN 4 @NSC‐500 executes excellent 4e − ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN 4 sites and Co 2 P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn‐air battery (ZAB) assembled by Co 2 P/CoN 4 @NSC‐500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm −2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.