Monday, 13 November 2006 - 10:25 AM
28h

Structure and Transport in Pyrrolidinium- and Imidazolium- Tfsi Ionic Liquids Doped with Litfsi

Oleg Borodin, Materials Science and Engineering, University of Utah, 122 S. Central Campus Dr. Rm 304, Salt Lake City, UT 84112 and Grant D. Smith, Materials Science & Eng, University of Utah, 122 S. Central Campus Dr. Rm 304, Salt Lake City, UT 84112.

We present structure and dynamics of pure and doped with 0.25 mol LiTFSI N-methyl-N-propyl pyrrolidinium+TFSI- (mppy+TFSI-) and ethyl-methyl-imidazolium+TFSI- ionic liquids. The liquid density, ion self-diffusion coefficients and conductivity predicted by MD simulations were found to be in good agreement with experimental data, where available. The Li+ cations were found to be coordinated on average by slightly less than four oxygen atoms with each oxygen atom being contributed by a different TFSI- anion in both imidazolium and pyrrolidinum-based ionic liquids.  Significant lithium aggregation through up to three TFSI- anions bridging lithiums was observed (Li+…(O=S=O)m…Li+), m=1,2,3, particularly at lower temperatures where the lithium aggregates were found to be stable for tens of nanoseconds. Polarization of TFSI- anions is largely responsible for the formation of such lithium aggregates.  Li+ transport was found to occur primarily by exchange of TFSI- anions in the first solvation shell with a smaller (~30%) contribution also due to Li+ cations diffusing together with their first solvation shell. Conductivity contribution due to the Li+ cation in LiTFSI doped mppy+TFSI- ionic liquids was found to be greater than that for a model poly(ethylene oxide)(PEO)/LiTFSI polymer electrolyte but significantly lower than that for ethylene carbonate/LiTFSI liquid electrolyte.   Finally, the time-dependent shear modulus for the ionic liquids is compared with that for polymers and nonionic liquids


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