Configuration‐Engineered Zn ²⁺ Solvation for Directed Interfacial Chemistry in Aqueous Zinc Batteries

Uncontrolled desolvation of dynamically hydrated [Zn(H ₂ O) ₆ ] ²⁺ complexes constitute the primary bottleneck for reversible aqueous zinc‐ion batteries, leading to stochastic interfacial side reactions and unpredictable solid–electrolyte interphase formation. Herein, we propose a configuration‐engineering strategy to regulate the Zn ²⁺ primary solvation sheath. Guided by the molecular design principles, i.e., configuration‐defined chelation, intermediate coordination strength, and regulated interfacial chemistry, we construct a stable five‐membered chelating structure using cysteamine as a model additive. The defined chelate configuration effectively displaces coordinated water molecules, lowering the desolvation energy barrier and reshaping the interfacial electronic distribution. The chelated complex participates in interfacial reactions during cycling, contributing to the formation of an N/S‐enriched interfacial layer that synergistically suppresses water activity while maintaining highly homogenized Zn ²⁺ flux transport. Consequently, the Zn anode achieves an exceptional lifespan of over 2000 h with a significantly reduced nucleation overpotential. This work establishes a generalized configurational design for electrolyte engineering toward high‐performance aqueous zinc‐ion batteries.