Boosting Bifunctional Oxygen Electrocatalysis via FeCoNiCuMn High‐Entropy Alloy Encapsulated within N‐Doped Carbon Core–Shell Structures for High‐Performance Zinc–Air Batteries

The development of efficient bifunctional oxygen electrocatalysts is crucial for the advancement of rechargeable zinc–air batteries (ZABs). Herein, we report a novel core–shell structured high‐entropy alloy (HEA) catalyst (FeCoNiCuMn@NC) derived from a multimetal Prussian blue analog (PBA), which integrates FeCoNiCuMn HEA nanoparticles encapsulated within a porous nitrogen‐doped carbon network. FeCoNiCuMn@NC exhibits a well‐defined interconnected carbon framework with abundant mesopores and a high specific surface area. The multicomponent HEA core induces lattice distortion that modulates the electronic structure of N ‐doped carbon (NC) shell, optimizing the electrocatalytic activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Benefiting from the synergistic interplay between the HEA core and the N ‐doped carbon shell, the catalyst demonstrates outstanding bifunctional ORR/OER activity, with a half‐wave potential of 0.842 V for ORR and an overpotential of 400 mV at 10 mA cm −2 for OER. Moreover, the unique core–shell encapsulation structure effectively prevents nanoparticle agglomeration and protects the HEA core from corrosion in alkaline electrolyte, ensuring remarkable durability. As a demonstration of its practical potential, a ZAB incorporating the FeCoNiCuMn@NC air cathode achieves a peak power density of 135.8 mW cm −2 together with excellent rate capability and long‐term cycling stability. This work offers a rational design strategy for HEA‐based bifunctional electrocatalysts toward advanced energy storage devices.