Electronic Communication Between Single Atomic Nickel and Iron‐Nitrogen Species Promote the Bifunctional Oxygen Evolution and Reduction for Efficient Rechargeable Zinc‐Air Battery

Abstract The reversible oxygen evolution/reduction reaction (OER/ORR) have been recognized as the key electrochemical process for next‐generation energy conversion and storage (ECS) devices, such as fuel cells and metal‐air batteries. However, the intrinsic large overpotential barrier caused by oxygen‐containing intermediates (*OH, *O, and *OOH) greatly hamper the reaction kinetics of OER/ORR. In this work, a dual‐functional OER/ORR electrocatalyst composed of Ni single atomic sites and FeN 0.0324 nanoclusters within a unique core–shell structure of FeN 0.0324 @NiN 4 /C is constructed. Benefiting from the efficient synergistic electronic effect of single atomic Ni and FeN 0.0324 , the FeN 0.0324 @NiN 4 /C exhibits excellent electrocatalytic activities for OER with an overpotential of 258 mV at 10 mA cm −2 and ORR with a half‐wave potential (E 1/2 ) of 0.89 V. A liquid zinc‐air battery assembled by FeN 0.0324 @NiN 4 /C achieves a maximum peak power density of 180.9 mW cm −2 and cycle endurance stability of more than 150 h. Density functional theory (DFT) calculation indicates that the d ‐band center near the Fermi level of NiN 4 ‐FeN 4 is shifted more upward in comparison with pristine NiN 4 H, which effectively optimizes the adsorption of *O and alleviates the troublesome OER process. This study provides a new platform for the construction of new OER/ORR electrocatalysts in the field of energy storage devices.