Harnessing Stable Electrode–Electrolyte Interface/Interphase Dynamics via Electrolyte Additives: Rationalized Pathways to Practical Aqueous Zinc‐Ion Batteries

Abstract The commercialization trajectory of aqueous zinc‐ion batteries (AZIBs) faces critical challenges, including zinc dendrites, parasitic side reactions, and inadequate cycling stability. The electrode–electrolyte interface (EEI), serving as the nexus between macroscopic device performance and microscopic electrochemical processes, fundamentally dictates reaction pathways through solvation structure modulation. A comprehensive understanding of both cathode and anode interfacial chemistries is imperative, as expanding and stabilizing reactive interfaces can significantly enhance depth of discharge (DOD). With this in mind, this review synthesizes recent advancements in electrolyte additive‐mediated interface engineering for high‐energy‐density AZIBs. The fundamental principles and practical evaluation methodologies governing additive implementation are systematically examined, while remaining challenges and future research directions are delineating. The review further catalogs cutting‐edge characterization techniques and discusses performance assessment protocols spanning laboratory‐scale experiments to pilot‐scale standardization efforts. Through comparative analysis of diverse additive categories, the critical importance of establishing scientifically grounded screening paradigms and standardized evaluation metrics to accelerate technology maturation from fundamental research to industrial implementation is emphasized. Finally, a critical analysis is presented of the remaining obstacles that must be overcome for AZIB deployment under diverse practical conditions, and prospects are provided for advancing durable, high‐energy AZIB energy storage systems toward commercialization.