Self-standing single lithium ion conductor polymer network with pendant trifluoromethanesulfonylimide groups: Li diffusion coefficients from PFGSTE NMR |
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Authors: | G.T.M. Nguyen A.L. Michan A. Fannir M. Viallon C. Vancaeyzeele C.A. Michal F. Vidal |
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Affiliation: | 1. Laboratoire de Physicochimie des Polymères et des Interfaces (LPPI, I-MAT), University of Cergy-Pontoise, 95000 Cergy-Pontoise, France;2. Physics and Astronomy, University of British Columbia, Vancouver, BC V6T 1Z1, Canada |
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Abstract: | Solid electrolyte materials have the potential to improve performance and safety characteristics of batteries by replacing conventional solvent-based electrolytes. For this purpose, new candidate single ion conductor self-standing networks were synthesized with trifluoromethane-sulfonylimide (TFSI) lithium salt based monomer using poly(ethyleneglycol) dimethacrylate (PEGDM 750) as crosslinker. The highest ionic conductivity was 3.4 × 10−7 S cm−1 at 30 °C in the dry state. Thermal and mechanical analyses showed good thermal stability up to 190 °C and rubbery-like properties at ambient temperature. A direct relationship between ionic conductivity and glassy or rubbery state of the membranes was found. Vogel–Tammann–Fulcher behavior was observed in the dry state which is consistent with a lithium conductivity correlated with polymer chain mobility. By swelling the network in propylene carbonate, a self-standing electrolyte gel could be obtained with an ionic conductivity as high as 1 × 10−4 S cm−1 at 30 °C. The individual diffusion coefficients of mobile species in the material (19F and 7Li) were measured and quantified using pulsed-field gradient nuclear magnetic resonance (PFG-NMR). Diffusion coefficients for the most mobile components of the lithium cations and fluorinated anions at 100 °C in dry membranes have been found to be 3.4 × 10−8 cm2 s−1 and 2.1 × 10−8 cm2 s−1 respectively. |
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Keywords: | Polymer electrolyte Ionic conductivity Pulsed-field gradient nuclear magnetic resonance Diffusion coefficient Ion pairing |
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