Cross‐Component Coupling in Rechargeable Zinc‐Air Batteries: From Reaction Competition to Device Reversibility

ABSTRACT The rapid expansion of renewable energy and electrified systems is increasing the demand for safe, low‐cost, and resource‐sustainable energy storage. Rechargeable zinc‐air batteries are promising because they combine abundant Zn, aqueous electrolytes, and an air‐fed oxygen electrode, yet their long‐term reversibility is constrained by coupled oxygen reactions, Zn chemistry, species transport, interfacial evolution, and finite material inventories. This review develops an operating‐state‐resolved framework linking reaction‐pathway competition during discharge, charge, and rest with shared‐electrolyte transport, electrode reversibility, cross‐component coupling, inventory retention, and device reversibility. An evidence hierarchy distinguishes direct operando or component‐resolved observations from correlation, mechanistic inference, and cross‐system analogy, while practical evaluation is considered under explicit load, Zn utilization, electrolyte inventory, gas environment, cumulative output, maintenance, and failure boundaries. These elements are further integrated into reaction‐selectivity‐oriented cross‐component co‐design. The resulting framework specifies the evidence needed to attribute failure, compares cycling claims within declared load and inventory boundaries, and identifies conditions under which air‐electrode, electrolyte, and Zn‐interface modifications can remain compatible.