Structural Design and Active‐Site Modulation of Bifunctional Electrocatalysts and Electrolyte Chemistry for Zinc–Air Batteries

Abstract Rechargeable zinc–air batteries (ZABs) have demonstrated considerable potential for commercial application due to their exceptional theoretical energy density, cost‐effectiveness, environmental compatibility, and safe reliability. However, their large‐scale application is restricted by sluggish kinetics in oxygen evolution (OER) and oxygen reduction (ORR) reactions as well as zinc dendrite formation. Therefore, the exploitation of high‐performance electrocatalyst and electrolyte represents a fundamental objective to facilitate reaction kinetics, cycling stability, and charge transfer efficiency. Bifunctional catalysts including precious metal nanoparticles, carbon composites, high‐entropy alloys, transition metal compounds, and single‐atom catalysts can exhibit tailored electronic structures and bifunctional reactivity for both ORR/OER processes. The rational design of these catalysts can provide new avenues for optimizing their fine structure and enhancing catalytic activity. The well‐known design principles for electrocatalytic materials such as d ‐band center theory, spin‐state optimization, orbital hybridization, and magnetic field‐assisted charge redistribution can provide effective guidelines to optimize adsorption energetics and accelerate reaction dynamics. Herein, this review summarizes the state‐of‐the‐art electrocatalyst design strategies, and elucidates the structure‐activity relationships from theoretical and experimental insights. Optimization schemes for efficient electrolytes are explored, aiming to offer valuable guidance and profound understanding for developing highly efficient Zn–air batteries.