Coordination chemistry governing practical aqueous zinc batteries: From solvation-Shell reconstruction and interfacial complexation to failure-aware cell design

Abstract

Aqueous zinc batteries combine nonflammable electrolytes and abundant Zn with attractive cost and safety, yet practical cells remain limited by chemistry that spans the Zn 2+ solvation shell, the electric double layer, and both electrode interfaces. This review develops a coordination-centered, failure-aware framework that connects ligand exchange, ion pairing, hydrogen-bond organization, adsorption, desolvation, nucleation, crystallographic growth, and coordination-derived interphases to Zn inventory loss and full-cell failure. We distinguish true coordination effects from correlated physical phenomena such as wetting, electrostatic screening, and surface-tension changes, and evaluate mechanistic claims using spectroscopy, operando imaging, gas analysis, electrochemical mass balance, molecular simulation, and data-driven models. Conflicting reports on Zn(002), Zn(100), and Zn(101) textures are reconciled as interface- and flux-dependent stability–kinetics trade-offs rather than a universal facet ranking. Particular emphasis is placed on limited-Zn and anode-free configurations, cathode-derived cross-talk, proton activity and local pH, and the mismatch between long-lived symmetric cells and practical full cells. Quantitative descriptors are compared against current/areal-capacity pairs, cumulative plated capacity, Zn depth of discharge, cathode loading, N/P and E/C ratios, calendar stability, pouch-cell scale, cost, and sustainability. The resulting coordination-to-device map defines the evidence needed to translate molecular regulation into durable, inventory-efficient aqueous Zn batteries.