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Insight View of Lithium Doped Imidazolium-Based Ionic Liquids in Presence of Organic Additive
The study has been carried out on in function of the temperature on the four samples C1C6ImNTf2, C1C6ImNTf2//VC (5%vol.) C1C6ImNTf2//LiNTf2 (1mol.L-1) and C1C6ImNTf2//VC(5% vol.)//LiNTf2 (1mol.L-1), by NMR using {1H-7Li}, {1H-19F} NOE correlations (HOESY), and pulsed field gradient spin-echo (PGSE) NMR. In neat IL and in IL//VC media, the diffusion coefficients follow the general trend reported in the literature (6), with a the slowest diffusion of [Li+] ions explained by the formation of a Li-anion aggregates, [Li(NTf2)n](n-1)-(7). On contrary, the diffusion coefficient of VC is remarkably decreasing in the presence of [Li+] ions. Moreover, the ratio of diffusion coefficients (D1/D2) was 4 time more the ratio of the viscosities (ŋ2:ŋ1), of the electrolyte C1C6ImNTf2//LiNTf2 (ŋ2,D2) and the neat IL (ŋ1,D1), suggesting a strong interaction/coordination of VC with [Li+] ions. Furthermore, 2D {1H-7Li} NOE correlations (HOESY) prove the vicinity of Li and VC. Both sets of experiments could be explained by the presence of VC in the coordination sphere of [Li+]. This potential formation of a VC-[Li+] interaction/coordination could have a major influence on the observed electrochemical behaviour of theses batteries. Since i) the D[Li+] is expected to increase because of the larger diffusivity of VC compared to [NTf2−] anion , and ii) also the activation energy for [Li+] ions diffusion is likely to increase, due to a somewhat more complicated diffusion mechanisms based on Borodin’ work, passing through Li-[NTf2−] complex diffusion, disruption, Li-VCcomplex formation etc. as depicted in Scheme 1.
Acknowledgements:
E.B. thanks to the financial support by COST Action Number CM1206 EXIL - Exchange on Ionic Liquids for STSM STSM-CM1206-14833 grant.
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