Solid-State NMR of the Family of Positive Electrode Materials Li2Ru1鈥?i>ySnyO3 for Lithium-Ion Batteries

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• 作者：Elodie Salager ; Vincent Sarou-Kanian ; M. Sathiya ; Mingxue Tang ; Jean-Bernard Leriche ; Philippe Melin ; Zhongli Wang ; Herv茅 Vezin ; Catherine Bessada ; Michael Deschamps ; Jean-Marie Tarascon
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：December 23, 2014
• 年：2014
• 卷：26
• 期：24
• 页码：7009-7019
• 全文大小：684K
• ISSN：1520-5002

文摘

The possibilities offered by ex situ and in situ operando ⁷Li solid-state nuclear magnetic resonance (NMR) are explored for the Li₂Ru_1鈥?i>ySn_yO₃ family (0 < y < 1), shown previously to display cationic and anionic redox activity when used as a positive electrode for Li ion batteries. Ex situ NMR spectroscopic studies indicate a nonrandom Sn/Ru substitution in the family. In the first charge, an increased metallicity at 4 V is deduced from the NMR spectra. Surprisingly, no striking difference is observed at 4.6 V compared to the pristine electrode, although the electronic structure is expected to be very different and the local cation environment to be distorted. For in situ operando measurements, we designed a new electrochemical cell that is compatible with NMR spectroscopy and one-dimensional magnetic resonance imaging (MRI). These operando measurements validate the ex situ observations and indicate that the environment formed at 4 V is specific of the initial charge and that there is little, if no, electrolyte decomposition, even at 4.6 V. This is another attractive feature of these compounds.