Synergistic Cation Solvation Reorganization and Fluorinated Interphase for High Reversibility and Utilization of Zinc Metal Anode

Batteries based on zinc (Zn) chemistry offer a great opportunity for large-scale applications owing to their safety, cost-effectiveness, and environmental friendliness. However, the poor Zn reversibility and inhomogeneous electrodeposition have greatly impeded their practical implementation, stemming from water-related passivation/corrosion. Here, we present a multifunctional electrolyte comprising gamma-butyrolactone (GBL) and Zn(BF4)2·xH2O to resolve these intrinsic challenges. The systematic results confirm that water reactivity toward a Zn anode is minimized by forcing GBL solvents into the Zn2+ solvation shell and constructing a fluorinated interphase on the Zn anode surface via anion decomposition. Furthermore, NMR was selected as an auxiliary testing protocol to elevate and understand the role of electrolyte composition in building the interphase. The combined factors in synergy guarantee high Zn reversibility (average Coulombic efficiency is 99.74%), high areal capacity (55 mAh/cm2), and high Zn utilization (∼91%). Ultimately, these merits enable the Zn battery utilizing a VO2 cathode to operate smoothly over 5000 cycles with a low-capacity decay rate of ∼0.0083% per cycle and a 0.23 Ah VO2/Zn pouch cell to operate over 400 cycles with a capacity retention of 77.3%.