Less is More: Underlying Mechanism of Zn Electrode Long‐Term Stability using Sodium L‐Ascorbate as Electrolyte Additive

Abstract Structured passivation layers and hydrated Zn²⁺ solvation structure strongly influence Zn depositions on Zn electrodes and then the cycle life and electrochemical performance of aqueous zinc ion batteries. To achieve these, the electrolyte additive of sodium L‐ascorbate (Ass) is introduced into aqueous zinc sulfate (ZnSO₄, ZS) electrolyte solutions. Combined experimental characterizations with theoretical calculations, the unique passivation layers with vertical arrayed micro‐nano structure are clearly observed, as well as the hydrated Zn²⁺ solvation structure is changed by replacing two ligand water molecules with As⁻, thus regulating the wettability and interfacial electric field intensity of Zn surfaces, facilitating rapid ionic diffusions within electrolytes and electrodes together with the inhibited side reactions and uniform depositions of Zn²⁺. When tested in Zn||Zn symmetric cell, the electrolyte containing Ass is extraordinarily stably operated for the long time ≈3700 h at both 1 mA cm⁻² and 1 mAh cm⁻². In Zn||MnO₂ full coin cells, the energy density can still maintain as high as ≈184 Wh kg⁻¹ at the power density high up to 2 kW kg⁻¹, as well as the capacity retention can reach up to 80.5% even after 1000 cycles at 2 A g⁻¹, which are substantially superior to the control cells.