title: Computational and experimental investigation of Li-doped ionic liquid electrolytes: [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4].
abstract: We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 ≤ xLi(+) ≤ 0.33) and temperature (298 K ≤ T ≤ 393 K). Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi(+) we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD simulations and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi(+), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi(+) = 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 and 0.3 mS/cm. Our transport results also demonstrate the necessity of long MD simulation runs (∼200 ns) to converge transport properties at room temperature. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions (τ(Li/-)), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li(+) transport in each liquid, we find that while the net motion of Li(+) with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange increases at high xLi(+) and in liquids with large anions.
authors.affiliation: ERC Inc., Thermal Protection Materials and Systems Branch, ‡Entry Systems and Technology Division, and §Thermal Protection Materials and Systems Branch, NASA Ames Research Center , Moffett Field, California 94035, United States.
authors.forename: Justin B
authors.initials: JB
authors.lastname: Haskins
authors.forename: William R
authors.initials: WR
authors.lastname: Bennett
authors.forename: James J
authors.initials: JJ
authors.lastname: Wu
authors.forename: Dionne M
authors.initials: DM
authors.lastname: Hernández
authors.forename: Oleg
authors.initials: O
authors.lastname: Borodin
authors.forename: Joshua D
authors.initials: JD
authors.lastname: Monk
authors.forename: Charles W
authors.initials: CW
authors.lastname: Bauschlicher
authors.forename: John W
authors.initials: JW
authors.lastname: Lawson