In Situ Construction of Zinc‐Mediated Fe, N‐Codoped Hollow Carbon Nanocages with Boosted Oxygen Reduction for Zn–Air Batteries

The rational design of bifunctional oxygen electrocatalysts with unique morphology and luxuriant porous structure is significant but challenging for accelerating the reaction kinetics of rechargeable Zn–air batteries (ZABs). Herein, zinc‐mediated Fe, N‐codoped carbon nanocages (Zn‐FeNCNs) are synthesized by pyrolyzing the polymerized iron‐doped polydopamine on the surface of the ZIF‐8 crystal polyhedron. The formation of the chelate between polydopamine and Fe serves as the covering layer to prevent the porous carbon nanocages from collapsing and boosts enough exposure and utilization of metal‐based active species during carbonization. Furthermore, both the theoretical calculation and experimental results show that the strong interaction between polyhedron and polydopamine facilitates the evolution of high‐activity zinc‐modulated FeNx sites and electron transportation and then stimulates the excellent bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). As expected, the Zn–air battery with Zn‐FeNCNs as an air cathode displays a superior power density (256 mW cm−2) and a high specific capacity (813.3 mA h gZn−1), as well as long‐term stability over 1000 h. Besides, when this catalyst is applied to the solid‐state battery, the device exhibited outstanding mechanical stability and a high round‐trip efficiency under different bending angles. A general template‐assisted method is employed for fabricating a zinc‐mediated Fe, N‐codoped carbon nanocages (Zn‐FeNCNs) bifunctional oxygen electrocatalyst. Owing to the synergistic effect of porous carbon nanocages, controllable electronic structure, and metal‐nitrogen active sites, the Zn–air battery assembled based on Zn‐FeNCNs catalyst displays a satisfactory powder density (256 mW cm−2) and extraordinary durability (1000 h, 3000 cycles).