Downloads: 375

Files in This Item:
File Description SizeFormat 
acs.jpcc.5b03273.pdf1.29 MBAdobe PDFView/Open
Title: Delithiation/lithiation behavior of LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> studied by in situ and ex situ <sup>6,7</sup>Li NMR spectroscopy
Authors: Shimoda, Keiji  kyouindb  KAKEN_id  orcid (unconfirmed)
Murakami, Miwa  kyouindb  KAKEN_id  orcid (unconfirmed)
Komatsu, Hideyuki
Arai, Hajime
Uchimoto, Yoshiharu  kyouindb  KAKEN_id  orcid (unconfirmed)
Ogumi, Zempachi
Author's alias: 下田, 景士
村上, 美和
荒井, 創
内本, 喜晴
小久見, 善八
Issue Date: 27-May-2015
Publisher: American Chemical Society
Journal title: Journal of Physical Chemistry C
Volume: 119
Issue: 24
Start page: 13472
End page: 13480
Abstract: Delithiation and lithiation behaviors of ordered spinel LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> and disordered spinel LiNi<inf>0.4</inf>Mn<inf>1.6</inf>O<inf>4</inf> were investigated by using in situ (in operando) <sup>7</sup>Li NMR and ex situ <sup>6</sup>Li MAS NMR spectroscopy. The in situ <sup>7</sup>Li monitoring of the ordered spinel revealed a clear appearance and subsequent disappearance of a new signal from the well-defined phase Li<inf>0.5</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf>, suggesting the two-phase reaction processes among Li<inf>1.0</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf>, Li<inf>0.5</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf>, and Li<inf>0.0</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf>. Also, for the disordered spinel, Li<inf>0.5</inf>Ni<inf>0.4</inf>Mn<inf>1.6</inf>O<inf>4</inf> was identified with a broad distribution in Li environment. High-resolution <sup>6</sup>Li MAS NMR spectra were also acquired for the delithiated and lithiated samples to understand the detailed local structure around Li ions. We suggested that the nominal Li-free phase Li<inf>0.0</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> can accommodate a small amount of Li ions in its structure. The tetragonal phases Li<inf>2.0</inf>Ni<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> and Li<inf>2.0</inf>Ni<inf>0.4</inf>Mn<inf>1.6</inf>O<inf>4</inf>, which occurred when the cell was discharged down to 2.0 V, were very different in the Li environment from each other. It is found that <sup>6, 7</sup>Li NMR is highly sensitive not only to the Ni/Mn ordering in LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> but also to the valence changes of Ni and Mn on charge-discharge process.
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in 'Journal of Physical Chemistry C', copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
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。
DOI(Published Version): 10.1021/acs.jpcc.5b03273
Appears in Collections:Journal Articles

Show full item record

Export to RefWorks

Export Format: 

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.