In this report, the lithium solvation behavior of two series of glyme-based electrolytes, with lithium trifluoromethanesulfonate (LiTf) or lithium-bis-(trifluormethanesulfonyl)-imide (LiTFSI) in six glymes with different chain length, is characterized using natural abundance oxygen-17 (17O) NMR spectroscopy. The effect of salt addition on chemical shift is observed by comparing the 17O NMR spectra of electrolytes and their corresponding neat solvents. The study reveals a more pronounced effect of the salt addition on the chemical shift of ether oxygens compared to terminal oxygens of glymes, thus suggesting a preferential coordination of Li+ with the ether oxygens. The 17O NMR data exhibit decreasing chemical shift changes with increasing chain length of glymes due to the increased number of ether oxygens coordinating each Li+ in the electrolytes. In addition, the trend of anion oxygen chemical shift, particularly for Tf- anion, suggests an effect of the chain length on the ion association degree. The results illustrate the sensitivity of 17O NMR to subtle changes in the ion-solvent and ion–ion interactions.
Natural abundance oxygen-17 NMR investigation of lithium ion solvation in glyme-based electrolytes / Peng, Jing; Carbone, Lorenzo; Gobet, Mallory; Hassoun, Jusef; Devany, Matthew; Greenbaum, Steven. - In: ELECTROCHIMICA ACTA. - ISSN 0013-4686. - STAMPA. - 213:(2016), pp. 606-612. [10.1016/j.electacta.2016.07.144]
Natural abundance oxygen-17 NMR investigation of lithium ion solvation in glyme-based electrolytes
CARBONE, LORENZO;HASSOUN, JUSEF;
2016
Abstract
In this report, the lithium solvation behavior of two series of glyme-based electrolytes, with lithium trifluoromethanesulfonate (LiTf) or lithium-bis-(trifluormethanesulfonyl)-imide (LiTFSI) in six glymes with different chain length, is characterized using natural abundance oxygen-17 (17O) NMR spectroscopy. The effect of salt addition on chemical shift is observed by comparing the 17O NMR spectra of electrolytes and their corresponding neat solvents. The study reveals a more pronounced effect of the salt addition on the chemical shift of ether oxygens compared to terminal oxygens of glymes, thus suggesting a preferential coordination of Li+ with the ether oxygens. The 17O NMR data exhibit decreasing chemical shift changes with increasing chain length of glymes due to the increased number of ether oxygens coordinating each Li+ in the electrolytes. In addition, the trend of anion oxygen chemical shift, particularly for Tf- anion, suggests an effect of the chain length on the ion association degree. The results illustrate the sensitivity of 17O NMR to subtle changes in the ion-solvent and ion–ion interactions.File | Dimensione | Formato | |
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