Functional‐Group Synergy Regulates Dynamic Hydrogen‐Bond for High‐Rate and Wide‐Temperature Zinc Deep Eutectic Electrolytes

ABSTRACT Zinc deep eutectic electrolytes (DEEs) have garnered increasing interest due to their unique physicochemical properties. However, simultaneously achieving high‐rate capability and wide‐temperature operation remains challenging because strong solvent–ion interactions increase both viscosity and desolvation barriers. Here, three model DEEs were constructed using propionamide, N ‐methylacetamide, and methylurea to systematically elucidate the roles of C═O, NH, and NH 2 functional groups in regulating salt dissociation and hydrogen‐bond networks. Comparative studies reveal that the cooperative C═O/NH groups govern efficient Zn‐salt dissociation, whereas the additional NH 2 group transforms a relatively rigid hydrogen‐bond network into a dynamically reconfigurable one. The resulting enhanced dynamic hydrogen‐bond exchange continuously reconstructs the Zn 2+ solvation environment, lowers the desolvation barrier, increases ligand participation in the primary solvation sheath, and promotes the formation of a robust N/Cl‐rich hybrid interphase. Consequently, the optimized ZCMI enables highly reversible Zn plating/stripping from −40°C to 60°C, sustains stable cycling for over 8000 h at −40°C, and supports current densities up to 10.0 mA·cm −2 . Zn||PANI full cells exhibit excellent rate capability, retain 96% of their initial capacity after 1200 cycles at −40°C, and operate stably at 60°C. These findings establish dynamic hydrogen‐bonding as a key descriptor governing solvation chemistry in zinc DEEs.