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. Issue 11 (1st November 2022) - Kawasaki, Mitsuo
Abstract : 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 Mg 2+ ions. In the resultant Li + /F – and Mg 2+ /F – hybrid electrolytes, Li2 F + and MgF + were the most probable soluble complexes, and the effective fluoride concentrations could reach ∼0.15 M along with excess Li + (Mg 2+ ) ions. Unique interactions between F – and Li + (Mg 2+ ) were observed using 19 F nuclear magnetic resonance spectroscopy. Li + (Mg 2+ ) 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.