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Title: 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
Authors: Kawasaki, Mitsuo
Morigaki, Ken-Ichi
Kano, Gentaro
Takekawa, Reiji
Kawamura, Junichi
Yokoyama, Yuko  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0002-3943-0978 (unconfirmed)
Kano, Kenji
Abe, Takeshi
Ogumi, Zempachi
Author's alias: 川﨑, 三津夫
森垣, 健一
狩野, 巌大郎
横山, 悠子
加納, 健司
安部, 武志
小久見, 善八
Issue Date: Nov-2022
Publisher: IOP Publishing Limited
The Electrochemical Society
Journal title: Journal of The Electrochemical Society
Volume: 169
Issue: 11
Thesis number: 110508
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 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.
Rights: © 2022 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited
This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited.
URI: http://hdl.handle.net/2433/278393
DOI(Published Version): 10.1149/1945-7111/ac9a05
Appears in Collections:Journal Articles

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