Polyphenol‐metal coordination derived high‐entropy alloy as bifunctional oxygen electrocatalyst for Zn‐air batteries

High‐entropy alloy (HEA) nanoparticles (NPs) have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties. Herein, we introduce Fe, Co, Ni, Cr and Mn into the metal‐polyphenol coordination system to prepare HEA NPs enclosed in N‐doped carbon (FeCoNiCrMn) with great potential for catalyzing oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The unique high‐entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species, leading to improved ORR ( E 1/2 = 0.89 V) and OER ( η = 330 mV, j = 10 mA·cm −2 ) activity. Additionally, FeCoNiCrMn exhibits excellent open‐circuit voltage (1.523 V), power density (110 mW·cm −2 ) and long‐term durability, outperforming Pt/C + IrO 2 electrodes as a cathode catalyst in Zn‐air batteries (ZABs). Such polyphenol‐assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high‐performance ZABs.