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Regulating the structure and composition of the lithium-ion (Li+) solvation shell is crucial to the performance of lithium metal batteries. The introduction of fluorine anions (F-) into the electrolyte significantly enhances the cycle efficiency and the interfacial stability of lithium metal anodes. However, the effect of dissolved F- on the solvation shell is rarely touched in the literature. Herein, we investigate the evolution processing of the fluorine-containing solvation structure to explore the underlying mechanisms via first-pri