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

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 1H, 7Li, and 19F 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 7Li and 19F pulsed‐field‐gradient (PFG) diffusion and 7Li longitudinal relaxation NMR measurements. Activation energies for ion diffusion were affected 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 stress‐induced local ordering. Centrifugal forces due to magic‐angle‐spinning (MAS) induce local chain ordering in a polymer electrolyte, yielding distributions in the local magnetic susceptibility tensor that result in characteristic lineshapes with doublet‐like splittings in subsequent static nuclear magnetic resonance (NMR) spectra. MAS‐induced local ordering had modest effects on pulsed‐field‐gradient (PFG) NMR measurements of ion diffusion coefficients and negligible effects on ion longitudinal relaxation rates. NMR researchers studying soft polymeric materials are encouraged to use only the spin rates necessary to achieve desired enhancements in sensitivity and resolution.