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

Reversable zinc‐air battery (ZAB) is a promising alternative for sustainable fuel cell, but the performance is impeded by the sluggish oxygen redox kinetics owing to the suboptimal adsorption and desorption of oxygen intermediates. Here, hetero‐TACs uniquely incorporate an electron regulatory role beyond the primary and secondary active sites found in dual‐atom catalysts. In‐situ XAFS and Raman spectroscopy elucidate Fe in FCN‐TM/NC functions as the main active site, leveraging long‐range electron coupling from neighbouring 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 FeN4 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.