How mixing tetraglyme with the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide changes volumetric and transport properties: An experimental and computational study

Journal Article · Wed Feb 01 00:00:00 EST 2017 · Chemical Engineering Science

DOI:https://doi.org/10.1016/j.ces.2016.05.006· OSTI ID:1543521

Sharma, Akash; Zhang, Yong; Gohndrone, Thomas; Oh, Seungmin; Brennecke, Joan F.; McCready, Mark J.; Maginn, Edward J.

The viscosity and density of the ionic liquid (IL) 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C6mim][NTf2]), the molecular solvent tetraethylene glycol dimethyl ether (tetraglyme or G4) and their binary mixtures were measured experimentally as a function of temperature. The same systems were also studied using classical molecular dynamics (MD) simulations. The viscosities of the [C6mim][NTf2]/G4 mixtures decrease with increasing G4 concentration, though not as much as an ideal mixing model would predict. Detailed analysis of the MD results reveals that G4 preferentially solvates cations, leading to a reduction in the interaction energy between cations and anions and a subsequent enhancement in anion mobility. A similar effect has been reported when glymes are mixed with salts containing alkali metal cations, with the resulting mixtures being called “solvate” ionic liquids. The simulations predict that the ionic conductivity will be maximized when the G4 mole fraction is around 10–20%. The ability of G4 to effectively solvate the cations stems from localized charges on the oxygen. The simulations predict that solvents having large localized positive charges would preferentially solvate anions, leading to enhanced cation mobility.

• Research Organization: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-05CH11231; AC02-06CH11357
• OSTI ID: 1543521
• Journal Information: Chemical Engineering Science, Vol. 159, Issue C; ISSN 0009-2509
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

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