Complexation of F^- by Li⁺ and Mg²⁺ Ions as Inorganic Anion Acceptors in Lactone-Based Li⁺/F^- and Mg²⁺/F^- Hybrid Electrolytes for Fluoride Shuttle Batteries

The development of high-quality fluoride-ion transporting electrolytes is a crucial demand for fluoride shuttle batteries (FSBs). However, the uncontrolled chemical and electrochemical activities of fluoride ions narrow the available potential window, hindering the development of high-voltage FSB cells. We present a method for upgrading recently developed lactone-based liquid fluoride electrolytes by complexation of F^- with Li⁺ and Mg²⁺ ions. In the resultant Li⁺/F^- and Mg²⁺/F^- hybrid electrolytes, Li₂F⁺ and MgF⁺ were the most probable soluble complexes, and the effective fluoride concentrations could reach ∼0.15 M along with excess Li⁺(Mg²⁺) ions. Unique interactions between F^- and Li⁺(Mg²⁺) were observed using ¹⁹F nuclear magnetic resonance spectroscopy. Li⁺(Mg²⁺) ions thus served as inorganic anion acceptors with ultimate redox stabilities to expand the negative potential window of the electrolytes to near −3 V vs SHE. The proposed complex formation was also supported by a conductometric titration method. We demonstrated the superior and versatile electrochemical performances of the Li⁺/F^- hybrid electrolyte, which enabled reversible charge/discharge reactions of various metal electrodes and composite electrodes in a wide range of redox series. Further, the Li⁺/F^- hybrid electrolyte opened valid new reaction paths for aluminum, making it a promising negative electrode in high-voltage FSB cells.