The physical properties of the ionic conductor, obtained by dissolution of lithium trifluoromethanesulphonylimide in polyethylene oxide, (PEO)nLi+((CF3SO2)2N)- have been investigated for several values of n. The phase diagram has been established from both DSC and NMR techniques. The diffusion coefficients of 7Li and 19F containing Species, determined by the pulsed magnetic field gradient (PMFG) technique, are interpreted as the measures of the cationic and anionic transport numbers, which are concentration dependent, and t+ reaches a value close to 0.3. This study is complemented by a systematic analysis of the behaviour of the 7Li relaxation time T1 versus temperature and concentration which is correlated to the glass temperature Tg.
The pulsed-field-gradient spin-echo NMR measurements have been performed on 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([emim][FSI]) and 1-ethyl-3-methylimidazolium [bis[(trifluoromethyl)sulfonyl]imide] ([emim][TFSI]) over a wide temperature range from 233 to 400 K. Molecular dynamics (MD) simulations have been performed on [emim][FSI], [emim][TFSI], [N-methyl-N-propylpyrrolidinium][FSI] ([pyr 13 ][FSI]), and [pyr 13 ][TFSI] utilizing a many-body polarizable force field. An excellent agreement between the ion self-diffusion coefficients from MD simulations and pfg-NMR experiments has been observed for [emim][FSI] and [emim][TFSI] ILs. The structure factor of [pyr 13 ][FSI], [pyr 14 ][TFSI], and [emim][TFSI] agreed well with the previously reported X-ray diffraction data performed by Umebayashi group. Ion packing in the liquid state is compared with packing in the corresponding ionic crystal. Faster transport found in the FSIbased ILs compared to that in TFSI-based ILs is associated with the smaller size of FSIanion and lower cation-anion binding energies. A significant artificial increase of the barriers (by 3 kcal/mol) for the FSIanion conformational transitions did not result in slowing down of ion transport, indicating that the ion dynamics is insensitive to the FSIanion torsional energetic, while the same increase of the TFSIanion barriers in [emim][TFSI] and [pyr 13 ][TFSI] ILs resulted in slowing down of the cation and anion transport by 40-50%. Details of ion rotational and translational motion, coupling of the rotational and translational relaxation are also discussed.
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