Hybrid Nanoalloy‐Cluster‐Single Atom Sites Based Aerophilic Carbon Fiber Membranes as Binder‐Free Cathodes for Ultra‐Long‐Life Zn‐air Batteries

Abstract High‐efficient and durable electrocatalysts for oxygen reduction and oxygen evolution reaction (ORR/OER) are desirable to Zn‐air batteries (ZABs). However, most of catalysts in powder form with sole active sites remain challenging in achieving the satisfactory bifunctional catalysis and suffer from peeling off during the long‐term operation. Herein, hybrid CoFe active sites are constructed containing nanoalloys (≈10 nm), clusters (< 2 nm), and single atoms on aerophilic carbon fiber membranes as binder‐free air cathodes for ultra‐long‐life ZABs. In particular, the high air‐permeability of membranes (0.2 s) can prevent the active sites from blocking by O₂ bubbles and promote the mass transfer. The theoretical and experimental results confirm that the hydrophilic CoFe₂O₄/CoFeOOH sites reconstructed on the surface of CoFe nanoalloys are mainly responsible for OER. While for single atoms and clusters on nitrogen (N)‐doped carbon matrix, they play a synergetic role in optimizing the adsorption energy to enhance ORR activity. Thus, the as‐prepared catalysts exhibit an ultra‐low ORR/OER potential gap (0.64 V). When further assembled as freestanding air‐electrodes, it exhibits an outstanding cycling lifespan of 1200 and 155 h in liquid‐ and quasi‐solid‐state ZABs respectively, which are fivefold and twofold higher than those of powder‐based cathodes (240/67 h).