Reconfiguring the Electrolyte Network Structure with Bio‐Inspired Cryoprotective Additive for Low‐Temperature Aqueous Zinc Batteries

Abstract Despite promising performance at ambient temperature, the development of aqueous zinc batteries is jeopardized by the freeze of aqueous electrolytes and deteriorative electrode‐electrolyte interphase at low temperatures. Herein, inspired by the cryoprotective mechanism of extracellular polysaccharides in biological organisms, a quaternized galactomannan polysaccharide (q‐GPA) is proposed as a cryoprotective additive for improving low‐temperature performance of aqueous zinc batteries. Mechanistic studies revealed that a multi‐hydroxyl galactomannan backbone can substantially attenuate the activity of water molecules through the reconfiguration of the hydrogen bond network, which inhibits ice crystal formation at subzero temperatures and thus depress the freezing point of the electrolyte. Meanwhile, the quaternary ammonium groups tethered on the q‐GPA skeleton are intended to neutralize the interfacial electric field through electrostatic repulsion, thereby accelerating Zn 2+ deposition kinetics and prohibiting zinc dendrite growth. Impressively, the q‐GPA–modified electrolyte enables an extended lifespan of over 1700 h in Zn||Zn symmetric battery at a high current density of 3 mA cm −2 and an ultralong cycle life of 5000 cycles with a capacity retention of 99.2% in the Zn||Na 2 V 6 O 16 ·1.5H 2 O (NVO) full battery at −30 °C. This work provides unprecedented possibilities for optimizing the electrolyte formulation of low‐temperature aqueous batteries.