Strong Replaces Weak: ​Hydrogen Bond‐Anchored Electrolyte Enabling Ultra‐Stable and Wide‐Temperature Aqueous Zinc‐Ion Capacitors

Abstract Despite aqueous electrolytes offer a great opportunity for large‐scale energy storage owing to their safety and cost‐effectiveness, their practical application suffers from the parasitic side reactions and poor temperature adaptability stemming from weak hydrogen‐bond (HB) network in free water. Here, we propose the guiding thought “strong replaces weak” to design hydrogen bond‐anchored electrolyte by introducing sulfolane (SL) for disrupting the regular weak HB network and contributing to superior temperature tolerance. Judiciously combined experimental characterization and theoretical calculation confirm that SL can remodel the primary solvation shell of metal ions, customize stable electrode interface chemistry and restrain the side reactions. Consequently, symmetric supercapacitor constructed by activated carbon (AC) electrodes is able to fully work within a voltage range of 2.4 V and reach high capacitance retention of 89.8 % after 60000 cycles. Additionally, Zn anodes exhibit ultra‐stable Zn plating/stripping behaviors and a wide temperature range (−20–60 °C), and zinc‐ion capacitor (Zn//AC) also delivers an excellent cycling stability with capacity retention of 99.7 % after 55000 cycles, implying that the designed electrolyte has practical application potential in extreme environments. This work proposes a novel critical solvation strategy that paves the route for the construction of ultra‐stable and wide‐temperature aqueous energy storage devices.