Fluoride-Rich, Organic–Inorganic Gradient Interphase Enabled by Sacrificial Solvation Shells for Reversible Zinc Metal Batteries

Zinc metal batteries are strongly hindered by water corrosion, as solvated zinc ions would bring the active water molecules to the electrode/electrolyte interface constantly. Herein, we report a sacrificial solvation shell to repel active water molecules from the electrode/electrolyte interface and assist in forming a fluoride-rich, organic-inorganic gradient solid electrolyte interface (SEI) layer. The simultaneous sacrificial process of methanol and Zn(CF₃SO₃)₂ results in the gradient SEI layer with an organic-rich surface (CH₂OC- and C₅ product) and an inorganic-rich (ZnF₂) bottom, which combines the merits of fast ion diffusion and high flexibility. As a result, the methanol additive enables corrosion-free zinc stripping/plating on copper foils for 300 cycles with an average coulombic efficiency of 99.5%, a record high cumulative plating capacity of 10 A h/cm² at 40 mA/cm² in Zn/Zn symmetrical batteries. More importantly, at an ultralow N/P ratio of 2, the practical VO₂//20 μm thick Zn plate full batteries with a high areal capacity of 4.7 mAh/cm² stably operate for over 250 cycles, establishing their promising application for grid-scale energy storage devices. Furthermore, directly utilizing the 20 μm thick Zn for the commercial-level areal capacity (4.7 mAh/cm²) full zinc battery in our work would simplify the manufacturing process and boost the development of the commercial zinc battery for stationary storage.