Inner-Sphere Penetration and Outer-Matrix Anchoring: A Biomimetic Compartmentalized Strategy for Sub-Zero Aqueous...

Aqueous zinc-ion batteries (AZIBs) are severely hindered at extremely low temperatures by aqueous electrolyte freezing, sluggish desolvation kinetics, and rampant dendrite growth. Drawing inspiration from biological compartmentalized cryoprotection, a biomimetic binary additive strategy is developed using penetrating dimethyl sulfoxide (DMSO) and non-penetrating raffinose. DMSO, functioning as a permeable additive, can infiltrate the primary solvation structure of zinc ions, modify the solvation sheath, and disturb the organized configuration of water molecules, thus impeding ice crystal formation. The non-permeable additive raffinose primarily modifies the surrounding microenvironments of the electrolyte, diminishing the activity of free water molecules, substantially decreasing the freezing point, and facilitating the system's shift to a glassy state. Consequently, the optimized electrolyte enables Zn//Zn symmetric cells to deliver an exceptional lifespan of 1600 h at 10 mA cm^-2, and maintain stable cycling over 600 h even at -30°C (5 mA cm^-2). Moreover, Zn//Cu half-cells achieve a high Coulombic efficiency of 99.76%, while Zn//NH₄V₄O₁₀ full cells retain 130 mAh g^-1 after 1000 cycles at -30°C and 5 A g^-1. This study breaks the low-temperature boundaries of AZIBs and offers a universal biomimetic paradigm for wide-temperature electrolyte engineering.