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Li+ Transport Mechanism in Oligo(Ethylene Oxide)s Compared to Carbonates

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Abstract

Molecular dynamics simulations have been performed on oligo(ethylene oxide)s of various molecular weights doped with the lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) in order to explore the mechanism of Li+ transport in materials covering the range from liquid electrolytes to prototypes for high molecular weight poly(ethylene oxide)-based polymer electrolytes. Good agreement between MD simulations and experiments is observed for the conductivity of electrolytes as a function of molecular weight. Unlike Li+ transport in liquid ethylene carbonate (EC) that comes from approximately equal contributions of vehicular Li+ motion (motion together with solvent) and Li+ diffusion by solvent exchange, Li+ transport in oligoethers was found to occur predominantly by vehicular motion. The slow solvent exchange of Li+ in oligo(ethylene oxide)s highlights why high molecular weight amorphous polymer electrolytes with oligo(ethylene oxide)s solvating groups suffer from poor Li+ transport. Ion complexation and correlation of cation and anion motion is examined for oligoethers and compared with that in EC.

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Authors and Affiliations

  1. Department of Materials Science & Engineering, University of Utah, 122 S. Central Campus Dr, Rm 304, Salt Lake City, UT, 84112-0560, USA

    Oleg Borodin & G. D. Smith

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  1. Oleg Borodin
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  2. G. D. Smith
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Correspondence to Oleg Borodin.

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Borodin, O., Smith, G.D. Li+ Transport Mechanism in Oligo(Ethylene Oxide)s Compared to Carbonates. J Solution Chem 36, 803–813 (2007). https://doi.org/10.1007/s10953-007-9146-1

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  • DOI: https://doi.org/10.1007/s10953-007-9146-1

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