Lithium salts dissolved in ionic liquids (ILs) are interesting alternatives to the commonly used electrolytes for Li-ion batteries. In this study, the solution of Li[bis-(trifluoromethanesulfonyl) (LiTFSI) in N-butyl-N-methyl-pyrrolidinium TFSI (PYR14TFSI) ionic liquid in the 0.1:0.9 molar ratio is studies by heteronuclear NOE and NMR diffusion measurements. The main purpose is to spot on the interions organization and mobility. NOF data support the existence of strongly coordinated Li+ species, whereas variable temperature measurements of the self-diffusion coefficients D show large, selective and unexpected enhancement of Li+ mobility with T. The measured activation energy for Li+ diffusion is significantly larger than those of TFSI+ and PHY14. These findings can be related to the mechanism of Li+ diffusion in ILs based on disruption formation of the coordination shells of Li+ with TFSI anions rather than on the Brownian motion of the whole Li coordinated species.
Molecular Environment and Enhanced Diffusivity of Li+ Ions in Lithium-Salt-Doped Ionic Liquid Electrolytes / F. Castiglione, E. M. Ragg, A. Mele, G.B. Appetecchi, M. Montanino, S. Passerini. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 2:3(2011 Feb 03), pp. 153-157. [10.1021/jz101516c]
Molecular Environment and Enhanced Diffusivity of Li+ Ions in Lithium-Salt-Doped Ionic Liquid Electrolytes
E.M. RaggSecondo
;
2011
Abstract
Lithium salts dissolved in ionic liquids (ILs) are interesting alternatives to the commonly used electrolytes for Li-ion batteries. In this study, the solution of Li[bis-(trifluoromethanesulfonyl) (LiTFSI) in N-butyl-N-methyl-pyrrolidinium TFSI (PYR14TFSI) ionic liquid in the 0.1:0.9 molar ratio is studies by heteronuclear NOE and NMR diffusion measurements. The main purpose is to spot on the interions organization and mobility. NOF data support the existence of strongly coordinated Li+ species, whereas variable temperature measurements of the self-diffusion coefficients D show large, selective and unexpected enhancement of Li+ mobility with T. The measured activation energy for Li+ diffusion is significantly larger than those of TFSI+ and PHY14. These findings can be related to the mechanism of Li+ diffusion in ILs based on disruption formation of the coordination shells of Li+ with TFSI anions rather than on the Brownian motion of the whole Li coordinated species.File | Dimensione | Formato | |
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