The key to realizing the application of aqueous electrolytes to extreme environments lies in rational constraints on active water. Herein, a strategy for local aggregation electrolyte (LA-Zn(OTf)2) with dynamic anchoring of active H2O is proposed and achieved by precisely regulating the molecular weight and addition amount of organic long chains enriched with hydrogen-bond acceptors. The results show that the saturated vapor pressure of LA-Zn(OTf)2 is reduced by 16% at 90°C and it does not freeze at -30°C, achieving a wide operating temperature range of 120°C. In LA-Zn(OTf)2, the local aggregation of Zn2+, solvent water, and ether bonding groups form a contact ion pair (CIP) structure, which enables rapid and stable deposition of Zn metal. Moreover, a stable organic-inorganic solid electrolyte interface (SEI) is formed to suppress corrosion and hydrogen evolution. At room temperature, the Zn|LA-Zn(OTf)2|Zn symmetric cell is stably cycled for over 4000 h at 1 mA cm-2. At the extreme temperatures of 90 and -30°C, the Zn|LA-Zn(OTf)2|NVO full cells achieve stable cycling more than 1400 and 2000 cycles at 0.5 A g-1, respectively, and the capacity retention rates are 70.1% and 80.5%, respectively.
