Examining Concentration‐Reliant Zn Deposition/Stripping Behavior in Organic Alcohol/Sulfones‐Modified Aqueous Electrolytes

The practical application of Zn metal anodes in electronic devices is hindered by dendrite growth and parasitic reactions. Electrolyte optimization, particularly the introduction of organic co-solvents, is widely used to circumvent these challenges. Various organic solvents in a wide range of concentrations have been reported; however, their influences and corresponding working mechanisms at different concentrations are largely unexplored in the same organic species. Herein, economical, low-flammable ethylene glycol (EG) is used as a model co-solvent in aqueous electrolytes to examine the relationship between its concentration, anode-stabilizing effect, and mechanism. Two maximal values are observed for the lifetime of Zn/Zn symmetric batteries under EG concentrations from 0.05 vol% to 48 vol%. Zn metal anodes can stably run for over 1700 h at a low EG content (0.25 vol%) and high EG content (40 vol%). Based on the complementary experimental and theoretical calculations, the enhancements in low- and high-content EG are ascribed to the specific surface adsorption for suppressed dendrite growth and the regulated solvation structure for inhibited side reactions, respectively. Intriguingly, a similar concentration-reliant bimodal phenomenon is observed in other low-flammable organic solvents (e.g., glycerol and dimethyl sulfoxide), thereby suggesting universality of this study and providing insight into electrolyte optimization.