title: Li+ transport in lithium sulfonylimide-oligo(ethylene oxide) ionic liquids and oligo(ethylene oxide) doped with LiTFSI.
abstract: The Li+ environment and transport in an ionic liquid (IL) comprised of Li+ and an anion of bis(trifluoromethanesulfonyl)imide anion (TFSI-) tethered to oligoethylene oxide (EO) (EO(12)TFSI-/Li+) were determined and compared to those in a binary solution of the oligoethylene oxide with LiTFSI salt (EO(12)/LiTFSI) by using molecular dynamics (MD) simulations and AC conductivity measurements. The latter revealed that the AC conductivity is 1 to 2 orders of magnitude less in the IL compared to the oligoether/salt binary electrolyte with greater differences being observed at lower temperatures. The conductivity of these electrolytes was accurately predicted by MD simulations, which were used in conjunction with a microscopic model to determine mechanisms of Li+ transport. It was discerned that structure-diffusion of the Li+ cation in the binary electrolyte (EO(12)/LiTFSI-) was similar to that in EO(12)TFSI-/Li+ IL at high temperature (>363 K), thus, one can estimate conductivity of IL at this temperature range if one knows the structure-diffusion of Li+ in the binary electrolyte. However, the rate of structure-diffusion of Li+ in IL was found to slow more dramatically with decreasing temperature than in the binary electrolyte. Lithium motion together with EO(12) solvent accounted for 90% of Li+ transport in EO(12)/LiTFSI-, while the Li+ motion together with the EO(12)TFSI- anion contributed approximately half to the total Li+ transport but did not contribute to the charge transport in IL.
authors.affiliation: Department of Materials Science & Engineering, 122 South Central Campus Drive, Room 304, University of Utah, Salt Lake City, Utah 84112-0560, USA. oleg.borodin@utah.edu
authors.forename: Oleg
authors.initials: O
authors.lastname: Borodin
authors.forename: G D
authors.initials: GD
authors.lastname: Smith
authors.forename: Olt
authors.initials: O
authors.lastname: Geiculescu
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Creager
authors.forename: Boutros
authors.initials: B
authors.lastname: Hallac
authors.forename: Darryl
authors.initials: D
authors.lastname: DesMarteau