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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 https://orcid.org/0000-0003-4800-3158 (unconfirmed) Orikasa, Yuki Matsumoto, Kazuhiko https://orcid.org/0000-0002-0770-9210 (unconfirmed) Hagiwara, Rika 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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