Conditions Extrêmes et Matériaux : Haute Température et Irradiation

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R.J.Messinger, T.V.Huynh, R.Bouchet, V.Sarou-Kanian, M.Deschamps, 'Magic-Angle-Spinning-Induced Local Ordering in Polymer Electrolytes and Its Effects on Solid-State Diffusion and Relaxation NMR Measurements', Magn. Reson. Chem. 58(11) 1118-1129 (2020) doi:10.1002/mrc.5033

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 pressures that may a ffect the physical state of soft materials, such as polymers, and subsequent solid-state NMR measurements. Here, we investigate the e ffects 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 stresses associated with MAS induce local chain ordering, which manifests itself as characteristic lineshapes with doublet-like splittings in subsequent solid-state 1H, 7Li, and 19F static NMR spectra characterizing the PEO chains and solvated ions. MAS results in distributions of stresses that hence local chain orientations and extents of chain alignments, yielding distributions in the local magnetic susceptibility tensor that give rise to the observed NMR anisotropy and lineshapes. The effect s of MAS were investigated on solid-state 7Li and 19F pulsed-field-gradient (PFG) and 7Li longitudinal NMR relaxation measurements. Activations energies for ion diff usion were a ffected modestly by MAS. 7Li 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 MAS-induced local ordering.