TY - JOUR
T1 - Reorientation Times for Solid-State Electrolyte Solvents and Electrolytes from NMR Spin-Lattice Relaxation Studies
AU - Davidowski, S. K.
AU - Yarger, J. L.
AU - Richert, R.
AU - Angell, C. A.
N1 - Funding Information:
This work was supported by the Department of Defense (DOD) Army Research Office (ARO) under Grant W911-NF19-10152. J.L.Y. acknowledges support from the National Science Foundation (NSF-DMR-BMAT-1809645) and the DOD Air Force Office of Scientific Research (AFOSR) under Award FA9550-17-1-0282. The authors appreciate helpful discussions with Peter Lunkenheimer.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/5/7
Y1 - 2020/5/7
N2 - Ionic and molecular plastic crystals have been studied recently as solid electrolytes or solvents, but the specific role of molecular reorientation has not been clarified. We use NMR spin-lattice relaxation times (T1 minima) to compare the time scale for magnetic fluctuations in a plastic crystal solvent to the molecular reorientation times, as established by dielectric spectroscopy. We focus on a mixture of succinonitrile and glutaronitrile, in which the rotationally disordered phase is stabilized against crystallization. Reorientation times can then be studied over 13 orders of magnitude, down to the glass transition temperature at 144 K. For each nucleus, 1H and 13C, the most probable magnetic fluctuation time is found to be slightly shorter than the reorientation time, but with practically indistinguishable temperature dependence. This facilitates investigation of the relation of solvent reorientation to ion conductivity relaxation times in ionic conducting systems in which the conductivity swamps the dielectric signature of solvent reorientation.
AB - Ionic and molecular plastic crystals have been studied recently as solid electrolytes or solvents, but the specific role of molecular reorientation has not been clarified. We use NMR spin-lattice relaxation times (T1 minima) to compare the time scale for magnetic fluctuations in a plastic crystal solvent to the molecular reorientation times, as established by dielectric spectroscopy. We focus on a mixture of succinonitrile and glutaronitrile, in which the rotationally disordered phase is stabilized against crystallization. Reorientation times can then be studied over 13 orders of magnitude, down to the glass transition temperature at 144 K. For each nucleus, 1H and 13C, the most probable magnetic fluctuation time is found to be slightly shorter than the reorientation time, but with practically indistinguishable temperature dependence. This facilitates investigation of the relation of solvent reorientation to ion conductivity relaxation times in ionic conducting systems in which the conductivity swamps the dielectric signature of solvent reorientation.
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U2 - 10.1021/acs.jpclett.0c00502
DO - 10.1021/acs.jpclett.0c00502
M3 - Article
C2 - 32242412
AN - SCOPUS:85084379484
SN - 1948-7185
VL - 11
SP - 3301
EP - 3304
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 9
ER -