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  • Title: Cation-anion interactions in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate-based ionic liquid electrolytes.
    Author: Burba CM, Rocher NM, Frech R, Powell DR.
    Journal: J Phys Chem B; 2008 Mar 13; 112(10):2991-5. PubMed ID: 18271572.
    Abstract:
    An important step in developing ionic-liquid-based electrolytes for lithium rechargeable batteries is obtaining a molecular-level understanding of the ionic interactions that occur in these systems. In this study, 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C2mim]CF3SO3) is complexed with LiCF3SO3, and the local structures of the CF3SO3- and [C2mim]+ ions are investigated with infrared and Raman spectroscopy. The isolation and subsequent refinement of a Li[C2mim](CF3SO3)2 crystal provides further insight into the structure of the [C2mim]CF3SO3-LiCF3SO3 solutions. Minor changes are observed in the infrared and Raman spectra of dilute [C2mim]CF3SO3-LiCF3SO3 solutions compared to pure [C2mim]CF3SO3. However, a suspension of very small Li[C2mim](CF3SO3)2 crystallites forms at a solution composition of [C2mim]CF3SO3:LiCF3SO3 = 10:1 (mole ratio), placing an upper limit on the solubility of LiCF3SO3. Essentially no changes are observed in the vibrational modes of the [C2mim]+ cations over the entire range of LiCF3SO3 compositions studied, suggesting that the addition of these compounds does not significantly perturb the local structure of the [C2mim]+ cations. The salt used in this study has a common anion with the ionic liquid; thus, the ion cloud surrounding the [C2mim]+ ions, which must be primarily composed of CF3SO3- anions, is not significantly altered with the addition of LiCF3SO3.
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