Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)
Abstract
The hexagonal mixed-anion solid solution Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1H and 23Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na2(CB9H10)(CB11H12) over the temperature range of 80-435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na+ jump process is characterized by the activation energy of 353(11) meV. Although Na+ mobility in Na2(CB9H10)(CB11H12) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na+ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na2(CB9H10)(CB11H12) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, bothmore »
- Authors:
-
- Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
- OSTI Identifier:
- 1542764
- Alternate Identifier(s):
- OSTI ID: 1529435
- Report Number(s):
- NREL/JA-5900-74309
Journal ID: ISSN 0925-8388
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Alloys and Compounds
- Additional Journal Information:
- Journal Volume: 800; Journal Issue: C; Journal ID: ISSN 0925-8388
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; energy storage materials; diffusion; nuclear resonances
Citation Formats
Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., and Udovic, T. J. Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12). United States: N. p., 2019.
Web. doi:10.1016/j.jallcom.2019.06.019.
Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., & Udovic, T. J. Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12). United States. https://doi.org/10.1016/j.jallcom.2019.06.019
Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., and Udovic, T. J. Wed .
"Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)". United States. https://doi.org/10.1016/j.jallcom.2019.06.019. https://www.osti.gov/servlets/purl/1542764.
@article{osti_1542764,
title = {Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)},
author = {Soloninin, A. V. and Skoryunov, R. V. and Babanova, O. A. and Skripov, A. V. and Dimitrievska, M. and Udovic, T. J.},
abstractNote = {The hexagonal mixed-anion solid solution Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1H and 23Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na2(CB9H10)(CB11H12) over the temperature range of 80-435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na+ jump process is characterized by the activation energy of 353(11) meV. Although Na+ mobility in Na2(CB9H10)(CB11H12) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na+ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na2(CB9H10)(CB11H12) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, both reorientational processes are found to be faster than the Na+ jump process responsible for the long-range diffusion.},
doi = {10.1016/j.jallcom.2019.06.019},
journal = {Journal of Alloys and Compounds},
number = C,
volume = 800,
place = {United States},
year = {Wed Jun 05 00:00:00 EDT 2019},
month = {Wed Jun 05 00:00:00 EDT 2019}
}
Web of Science