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タイトル: Phase Evolution of Trirutile Li₀.₅FeF₃ for Lithium-Ion Batteries
著者: Zheng, Yayun
Tawa, Shinya
Hwang, Jinkwang  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0003-4800-3158 (unconfirmed)
Orikasa, Yuki
Matsumoto, Kazuhiko  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0002-0770-9210 (unconfirmed)
Hagiwara, Rika  KAKEN_id  orcid https://orcid.org/0000-0002-7234-3980 (unconfirmed)
著者名の別形: 鄭, 亞雲
田和, 慎也
黄, 珍光
松本, 一彦
萩原, 理加
キーワード: Electrodes
Chemical structure
Physical and chemical processes
Electrolytes
Materials
発行日: Feb-2021
出版者: American Chemical Society (ACS)
誌名: Chemistry of Materials
巻: 33
号: 3
開始ページ: 868
終了ページ: 880
抄録: Extensive studies on trirutile Li₀.₅FeF₃ phase have been commissioned in the context of the Li–Fe–F system for Li-ion batteries. However, progress in electrochemical and structural studies has been greatly encumbered by the low electrochemical reactivity of this material. In order to advance this class of materials, a comprehensive study into the mechanisms of this phase is necessary. Therefore, herein, we report for the first time overall reaction mechanisms of ordered trirutile Li₀.₅FeF₃ at elevated temperatures of 90 °C with the aid of a thermally stable ionic liquid electrolyte. Ordered trirutile Li₀.₅FeF₃ is prepared by high-energy ball milling combined with heat treatment followed by electrochemical tests, X-ray diffraction, and X-ray absorption spectroscopic analyses. Our results reveal that a reversible topotactic Li⁺ extraction/insertion from/into the trirutile structure occurs in a two-phase reaction with a minor volume change (1.09% between Li₀.₅FeF₃ and Li₀.₁₁FeF₃) in the voltage range of 3.2–4.3 V. The extension of the lower cutoff voltage to 2.5 V results in a conversion reaction to LiF and rutile FeF₂ during discharging. The subsequent charge triggers the formation of the disordered trirutile structure at 4.3 V without showing the reconversion from LiF and rutile FeF₂ to ordered trirutile Li₀.₅FeF₃ or FeF₃.
著作権等: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.0c03544.
The full-text file will be made open to the public on 9 February 2022 in accordance with publisher's 'Terms and Conditions for Self-Archiving'.
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
URI: http://hdl.handle.net/2433/265329
DOI(出版社版): 10.1021/acs.chemmater.0c03544
出現コレクション:学術雑誌掲載論文等

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