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Multinuclear NMR Study of Structure and Mobility in Cyclic Model Lithium Conducting Systems

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Abstract

The transport of the lithium ions is the basis of lithium ion conductivity of currently used electrolytes. Understanding how the transport of lithium ions within the matrix is influenced by the interactions with solvating moieties is needed to improve their performance. Along these lines well-defined model compounds based on cyclotriphosphazene (CTP) and hexaphenylbenzene (HPB) cores, bearing side groups of ethylene carbonate, a common solvent for lithium salts used as electrolytes in Li-ion batteries (Thielen et al. Chem. Mater, 23, 2120, 2011) and blended with different amounts of Lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) have been studied by multinuclear nuclear magnetic resonance (NMR) spectroscopy. The local dynamics of the matrix was probed by 1H and 31P NMR, while the local dynamics of the Li+ cations was unraveled by 7Li and 13C NMR. Transport of both ions was studied by pulsed-field gradient (PFG) NMR. Based on the different temperature dependences of the dynamics the bulk ion transport is not attributed to local dynamics, but to translational diffusion best characterized by PFG NMR. Although the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The results of NMR spectroscopy are in accord with the conjecture that the coordination between the cyclic carbonate functionality and the Li+-ion is too tight to allow for fast ion dynamics.

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Acknowledgments

We thank W. H. Meyer and G. Brunklaus for helpful discussions of different aspects of this work. We further thank Sebastian Jeremias for practical assistance with the PFG NMR experiments.

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Authors and Affiliations

  1. Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany

    Jörg Thielen, Christoph F. Kins & Hans Wolfgang Spiess

  2. Institute of Physical Chemistry, University of Muenster, Corrensstr. 28/30, 48149, Münster, Germany

    Monika Schönhoff

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  1. Jörg Thielen
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  2. Christoph F. Kins
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  3. Monika Schönhoff
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  4. Hans Wolfgang Spiess
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Correspondence to Hans Wolfgang Spiess.

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Thielen, J., Kins, C.F., Schönhoff, M. et al. Multinuclear NMR Study of Structure and Mobility in Cyclic Model Lithium Conducting Systems. Appl Magn Reson 45, 1063–1073 (2014). https://doi.org/10.1007/s00723-014-0588-5

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  • DOI: https://doi.org/10.1007/s00723-014-0588-5

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