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EnglishIn 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.
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| Data di pubblicazione: | 2016 | |
| Titolo: | Natural Abundance Oxygen-17 NMR Investigation of Lithium Ion Solvation in Glyme-based Electrolytes | |
| Autori: | Peng, Jing; Carbone, Lorenzo; Gobet, Mallory; Hassoun, Jusef; Devany, Matthew; Greenbaum, Steven | |
| Rivista: | ELECTROCHIMICA ACTA | |
| Parole Chiave: | glymes; ion association; ion solvation; Lithium battery electrolytes; oxygen-17 NMR; Chemical Engineering (all); Electrochemistry | |
| Abstract in inglese: | 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. | |
| Digital Object Identifier (DOI): | 10.1016/j.electacta.2016.07.144 | |
| Handle: | http://hdl.handle.net/11392/2358467 | |
| Appare nelle tipologie: | 03.1 Articolo su rivista |
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