ABSTRACT Organic‐rich eutectic electrolytes, which have been prevalent to address the electrolyte freezing and Zn dendrite growth challenges for low‐temperature aqueous zinc‐based batteries, suffer from sluggish Zn 2+ desolvation kinetics and mass transport. Here, we introduce aprotic acetone as a cosolvent to improve the performance of aqueous Zn(BF 4 ) 2 ‐based electrolyte under cold environments. Leveraging dynamic keto‐enol tautomerism in the primary solvation sheath of Zn 2+ propelled by the electrical double layer electric field, an anion‐type solvation structure is established, which shortens the Zn 2+ desolvation path with accelerated kinetics and constructs a tough and tight interface with a gradient organic‐inorganic configuration, eventually enabling uniform Zn deposition at low temperatures. As a result, Zn||Zn symmetric cells sustain for 7500 h at 1 mA·cm −2 and over 1200 h with 34.2 % DOD at 10 mA·cm −2 under −40°C. Pouch‐cell properties are demonstrated by matching a PEDOT‐V 2 O 5 cathode, which harvests a high capacity of 150 mAh over 210 cycles under practical conditions (N/P = 4.33 and E/C = 6.0 µL mg −1 ) and holds approaching 100 % capacity retention at −40°C. This work provides an effective strategy toward industrializing practical cold‐resistant zinc‐based batteries via modulating the electrolyte structure.
Chen et al. (2026) studied this question.