Asymmetrical Triatomic Sites with Long‐Range Electron Coupling for Ultra‐Durable and Extreme‐Low‐Temperature Zinc–Air Batteries

Abstract Reversible zinc–air battery (ZAB) is a promising alternative for sustainable fuel cells, but the performance is impeded by the sluggish oxygen redox kinetics owing to the suboptimal adsorption and desorption of oxygen intermediates. Here, hetero‐trimetallic atom catalysts (TACs) uniquely incorporate an electron regulatory role beyond primary and secondary active sites found in dual‐atom catalysts. In situ X‐ray absorption fine structure (XAFS) and Raman spectroscopy elucidate Fe in FeCoNi SA catalyst (FCN‐TM/NC) functions as the main active site, leveraging long‐range electron coupling from neighboring Co and Ni to boost catalytic efficiency. The ZAB equipped with FCN‐TM/NC exhibits ultra‐stable rechargeability (over 5500 h at 1 mA cm −2 under −60 °C). The in‐depth theoretical and experimental investigations attribute such superior catalytic activity to the asymmetric FeN 4 configuration, long‐distance electron coupling, modulated local microenvironment, optimized d orbital energy levels, and lower energy barrier for bifunctional oxygen electrocatalysis. This work provides a comprehensive mechanistic understanding of the structure‐reactivity relationship in TACs for energy conversion.