期刊
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
卷 169, 期 11, 页码 -出版社
ELECTROCHEMICAL SOC INC
DOI: 10.1149/1945-7111/ac9a05
关键词
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资金
- New Energy and Industrial Technology Development Organization (NEDO) [JPNP16001, JPNP21006]
The development of high-quality fluoride-ion transporting electrolytes is crucial for the advancement of fluoride shuttle batteries. In this study, a promising method to enhance lactone-based liquid fluoride electrolytes was proposed by complexing F- with Li+ and Mg2+ ions. The resulting Li+/F- and Mg2+/F- hybrid electrolytes demonstrated exceptional electrochemical performances and expanded the negative potential window of the electrolytes, enabling new possibilities for high-voltage FSB cells.
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 similar to 0.15 M along with excess Li+(Mg2+) ions. Unique interactions between F- and Li+(Mg2+) were observed using F-19 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.
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