Aqueous Electrolytes with Hydrophobic Organic Cosolvents for Stabilizing Zinc Metal Anodes

Rechargeable aqueous zinc (Zn) batteries are promising for large-energy storage because of their low cost, high safety, and environmental compatibility, but their implementation is hindered by the severe irreversibility of Zn metal anodes as exemplified by water-induced side reactions (H₂ evolution and Zn corrosion) and dendrite growth. Here, we find that the introduction of a hydrophobic carbonate cosolvent into a dilute aqueous electrolyte exhibits a much stronger ability to address the reversible issues facing Zn anodes than that with hydrophilic ones. Among the typical carbonates (ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate (DEC)), DEC as the most hydrophobic additive enables the strongest breaking of water's H-bond network and replaces the solvating H₂O in a Zn²⁺-solvation sheath, which significantly reduces the water activity and its decomposition. Additionally, DEC molecules preferentially adsorb onto the Zn surface to create an H₂O-poor electrical double layer and render a dendrite-free Zn²⁺-plating behavior. The formulated hybrid 2 m Zn(OTf)₂ + 7 m DEC electrolyte endows the Zn electrode with an ability to achieve high cycling stability (over 3500 h at 5 mA cm^-2 with 2.5 mA h cm^-2) and supports the stable operation of Zn||V₂O₅·nH₂O full battery. This efficient strategy with hydrophobic cosolvent suggests a promising direction for designing aqueous battery chemistries.