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タイトル: Direct observation of layered-to-spinel phase transformation in Li2MnO3 and the spinel structure stabilised after the activation process
著者: Shimoda, Keiji
Oishi, Masatsugu
Matsunaga, Toshiyuki
Murakami, Miwa
Yamanaka, Keisuke
Arai, Hajime
Ukyo, Yoshio
Uchimoto, Yoshiharu
Ohta, Toshiaki
Matsubara, Eiichiro
Ogumi, Zempachi
著者名の別形: 下田, 景士
大石, 昌嗣
右京, 良雄
内本, 喜晴
松原, 英一郎
小久見, 善八
発行日: 2-May-2017
出版者: Royal Society of Chemistry
誌名: Journal of Materials Chemistry A
巻: 5
号: 14
開始ページ: 6695
終了ページ: 6707
抄録: Li2MnO3 is an important parent component in lithium- and manganese-rich layered oxides (LMRs), which are one of the promising positive electrode materials for next-generation lithium ion rechargeable batteries. Here, we report the layered-to-spinel phase transformation in Li2MnO3 during the initial charging process to characterise its unique delithiation behaviour, which gives an insight into the relationship between the structure, superior capacities and degradation of LMR electrodes. The atomic-scale observation using scanning transmission electron microscopy (STEM) techniques suggests that the structural transformation occurs in a biphasic manner within a single particle. The formed phase has a Li-defect spinel structure, indicating that the delithiation leads to Mn migration from the transition-metal layer to the Li layer, accompanied by some oxygen release. This layered-to-spinel phase transformation is an essential bulk process in the initial activation of Li2MnO3. During the lithiation in the 1st discharge, the Mn remigration occurs and the layered structure is again formed with significant disordering. During the multiple cycles, the defect spinel structure is stabilised and becomes more oxygen-deficient with a lower Mn valency. As a consequence, the amount of inserted Li decreases, which corresponds to the capacity and voltage fading observed in Li2MnO3 and LMRs.
著作権等: This is the accepted version of the article, which has been published in final form at http://dx.doi.org/10.1039/c6ta11151c.
The full-text file will be made open to the public on 02 May 2018 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/2433/224984
DOI(出版社版): 10.1039/c6ta11151c
出現コレクション:学術雑誌掲載論文等

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