Magic-angle-spinning-induced local ordering in polymer electrolytes and its effects on solid-state diffusion and relaxation NMR measurements

© 2020 John Wiley & Sons, Ltd.

Bibliographische Detailangaben
Veröffentlicht in:Magnetic resonance in chemistry : MRC. - 1985. - 58(2020), 11 vom: 16. Nov., Seite 1118-1129
1. Verfasser: Messinger, Robert J (VerfasserIn)
Weitere Verfasser: Vu Huynh, Tan, Bouchet, Renaud, Sarou-Kanian, Vincent, Deschamps, Michaël
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2020
Zugriff auf das übergeordnete Werk:Magnetic resonance in chemistry : MRC
Schlagworte:Journal Article Research Support, Non-U.S. Gov't diffusion magic-angle spinning magnetic susceptibility polymer electrolyte relaxation solid-state NMR
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520 |a Magic-angle-spinning (MAS) enhances sensitivity and resolution in solid-state nuclear magnetic resonance (NMR) measurements. MAS is obtained by aerodynamic levitation and drive of a rotor, which results in large centrifugal forces that may affect the physical state of soft materials, such as polymers, and subsequent solid-state NMR measurements. Here, we investigate the effects of MAS on the solid-state NMR measurements of a polymer electrolyte for lithium-ion battery applications, poly(ethylene oxide) (PEO) doped with the lithium salt LiTFSI. We show that MAS induces local chain ordering, which manifests itself as characteristic lineshapes with doublet-like splittings in subsequent solid-state 1 H, 7 Li, and 19 F static NMR spectra characterizing the PEO chains and solvated ions. MAS results in distributions of stresses and hence local chain orientations within the rotor, yielding distributions in the local magnetic susceptibility tensor that give rise to the observed NMR anisotropy and lineshapes. The effects of MAS were investigated on solid-state 7 Li and 19 F pulsed-field-gradient (PFG) diffusion and 7 Li longitudinal relaxation NMR measurements. Activation energies for ion diffusion were affected modestly by MAS. 7 Li longitudinal relaxation rates, which are sensitive to lithium-ion dynamics in the nanosecond regime, were essentially unchanged by MAS. We recommend that NMR researchers studying soft polymeric materials use only the spin rates necessary to achieve the desired enhancements in sensitivity and resolution, as well as acquire static NMR spectra after MAS experiments to reveal any signs of stress-induced local ordering 
650 4 |a Journal Article 
650 4 |a Research Support, Non-U.S. Gov't 
650 4 |a diffusion 
650 4 |a magic-angle spinning 
650 4 |a magnetic susceptibility 
650 4 |a polymer electrolyte 
650 4 |a relaxation 
650 4 |a solid-state NMR 
700 1 |a Vu Huynh, Tan  |e verfasserin  |4 aut 
700 1 |a Bouchet, Renaud  |e verfasserin  |4 aut 
700 1 |a Sarou-Kanian, Vincent  |e verfasserin  |4 aut 
700 1 |a Deschamps, Michaël  |e verfasserin  |4 aut 
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