Synergetic Regulation of Enthalpy‐Entropy via Dipole Interactions Enabling Textured and Low‐Temperature Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) suffer from severe H 2 O‐induced parasitic reactions and uneven Zn deposition, especially at sub‐zero temperatures. Herein, we propose a hydrated eutectic high‐entropy electrolyte based on Zn(ClO 4 ) 2 , ethylene glycol, 1,5‐pentanediol, and H 2 O, which couples a configurationally diverse bulk solvation environment with spatially differentiated interfacial regulation through synergistic enthalpy–entropy effects. Diversified solvation configurations promote the formation of an organic‐rich gradient hybrid solid electrolyte interphase, while enriched dipole–dipole interactions suppress H 2 O activity and strengthened ion‐dipole interactions provide kinetic buffering for Zn 2+ supply. Such coupled solvation and interfacial regulation enables interfacial deposition kinetics to be balanced with bulk ion migration, thereby homogenizing interfacial Zn 2+ flux, alleviating concentration polarization, and inhibiting dendritic growth. Moreover, preferential interfacial adsorption of organic species promotes the exposure of the Zn (002) plane, inducing thermodynamically favorable Zn (002) ‐oriented deposition. Consequently, Zn||Zn symmetric cells operate for over 2000 h at 25°C and over 3000 h at −20°C. Zn||PANI pouch cells achieve capacity retentions of 91.32% after 1200 cycles at 25°C and 98.65% after 2000 cycles at −20°C, while full cells cycle stably for 500 cycles at −50°C with negligible capacity decay. These findings highlight synergistic enthalpic‐entropic regulation as an effective strategy for developing durable wide‐temperature AZIBs.