Molecular‐Crowding Effect Mimicking Cold‐Resistant Plants to Stabilize the Zinc Anode with Wider Service Temperature Range

Growth of dendrites, the low plating/stripping efficiency of Zn anodes, and the high freezing point of aqueous electrolytes hinder the practical application of aqueous Zn‐ion batteries. Here, a zwitterionic osmolyte‐based molecular crowding electrolyte is presented, by adding betaine (Bet, a by‐product from beet plant) to the aqueous electrolyte, to solve the abovementioned problems. Substantive verification tests, density functional theory calculations, and ab initio molecular dynamics simulations consistently reveal that side reactions and growth of Zn dendrites are restrained because Bet can break Zn2+ solvation and regulate oriented 2D Zn2+ deposition. The Bet/ZnSO4 electrolyte enables superior reversibility in a Zn–Cu half‐cell to achieve a high Coulombic efficiency >99.9% for 900 cycles (≈1800 h), and dendrite‐free Zn plating/stripping in Zn–Zn cells for 4235 h at 0.5 mA cm−2 and 0.5 mAh cm−2. Furthermore, a high concentration of Bet lowers the freezing point of the electrolyte to −92 °C via the molecular‐crowding effect, which ensures the stable operation of the aqueous batteries at −30 °C. This innovative concept of such a molecular crowding electrolyte will inject new vitality into the development of multifunctional aqueous electrolytes. A molecular crowding electrolyte is developed for aqueous Zn‐ion batteries. Betaine in the electrolyte can regulate the solvation sheath of Zn2+ and adsorb on the Zn anode to guide the dendrite‐free deposition of Zn2+. A high concentration of betaine breaks the H‐bond between H2O, which keeps the Zn anode stable in a wide temperature range from −30 to 60 °C.