Suppressed Dissolution of Fluorine-Rich SEI Enables Highly Reversible Zinc Metal Anode for Stable Aqueous Zinc-Ion Batteries

The instability of the solid electrolyte interface (SEI) is a critical challenge for the zinc metal anodes, leading to an erratic electrode/electrolyte interface and hydrogen evolution reaction (HER), ultimately resulting in anode failure. This study uncovers that the fluorine species dissolution is the root cause of SEI instability. To effectively suppress the F- dissolution, an introduction of a low-polarity molecule, 1,4-thioxane (TX), is proposed, which reinforces the stability of the fluorine-rich SEI. Moreover, the TX molecule has a strong affinity for coordinating with Zn2+ and adsorbing at the electrode/electrolyte interface, thereby diminishing the activity of local water and consequently impeding SEI dissolution. The robust fluorine-rich SEI layer promotes the high durability of the zinc anode in repeated plating/stripping cycles, while concurrently suppressing HER and enhancing Coulombic efficiency. Notably, the symmetric cell with TX demonstrates exceptional electrochemical performance, sustaining over 500 hours at 20 mA cm-2 with 10 mAh cm-2. Furthermore, the Zn||KVOH full cell exhibits excellent capacity retention, averaging 6.8 mAh cm-2 with 98 % retention after 400 cycles, even at high loading with a lean electrolyte. This work offers a novel perspective on SEI dissolution as a key factor in anode failure, providing valuable insights for the electrolyte design in energy storage devices. Fluorine-rich SEI dissolution is a major cause of zinc anode failure. The SEI content fluctuates significantly during the plating/stripping process, resulting in an unstable electrode/electrolyte interface. A versatile functional electrolyte additive, thioether-TX was introduced to reduce solvent polarity, as a poor solvent molecule for F-. Additionally, TX could modulate the Zn2+ solvation structure and adsorb at the electrode/electrolyte interface to reduce the activity of local water, further suppressing the dissolution of ZnF2 and stabilizing the fluorine-rich SEI layer. image