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Title: Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates

The salt compounds NaB 11H 14, Na-7-CB10H13, Li-7-CB 10H 13, Na-7,8-C 2B 9H 12, and Na-7,9-C 2B 9H 12 all contain geometrically similar, monocharged, nido-undeca(carba)borate anions (i.e., truncated icosohedral-shaped clusters constructed of only 11 instead of 12 {B-H} + {C-H} vertices and an additional number of compensating bridging and/or terminal H atoms). We used first-principles calculations, X-ray powder diffraction, differential scanning calorimetry, neutron vibrational spectroscopy, neutron elastic-scattering fixed-window scans, quasielastic neutron scattering, and electrochemical impedance measurements to investigate their structures, bonding potentials, phase-transition behaviors, anion orientational mobilities, and ionic conductivities compared to those of their closo-poly(carba)borate cousins. All exhibited order-disorder phase transitions somewhere between room temperature and 375 K. All disordered phases appear to possess highly reorientationally mobile anions (> ~10 10 jumps s -1 above 300 K) and cation-vacancy-rich, close-packed or body-center-cubic-packed structures [like previously investigated closo-poly(carba)borates]. Moreover, all disordered phases display superionic conductivities but with generally somewhat lower values compared to those for the related sodium and lithium salts with similar monocharged 1-CB 9H 10- and CB 11H 12- closo-carbaborate anions. This study significantly expands the known toolkit of solid-state, poly(carba)borate-based salts capable of superionic conductivities and provides valuable insights into the effect of crystal lattice, unit cellmore » volume, number of carbon atoms incorporated into the anion, and charge polarization on ionic conductivity.« less
Authors:
 [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [4] ; ORCiD logo [4] ; ORCiD logo [3] ; ORCiD logo [4]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Report Number(s):
NREL/JA-5900-71251
Journal ID: ISSN 0897-4756
Grant/Contract Number:
AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 24; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; carbon; differential scanning calorimetry; electrochemical impedance spectroscopy; ionic conductivity; negative ions; neutron scattering
OSTI Identifier:
1431414

Tang, Wan Si, Dimitrievska, Mirjana, Stavila, Vitalie, Zhou, Wei, Wu, Hui, Talin, A. Alec, and Udovic, Terrence J.. Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates. United States: N. p., Web. doi:10.1021/acs.chemmater.7b04332.
Tang, Wan Si, Dimitrievska, Mirjana, Stavila, Vitalie, Zhou, Wei, Wu, Hui, Talin, A. Alec, & Udovic, Terrence J.. Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates. United States. doi:10.1021/acs.chemmater.7b04332.
Tang, Wan Si, Dimitrievska, Mirjana, Stavila, Vitalie, Zhou, Wei, Wu, Hui, Talin, A. Alec, and Udovic, Terrence J.. 2017. "Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates". United States. doi:10.1021/acs.chemmater.7b04332. https://www.osti.gov/servlets/purl/1431414.
@article{osti_1431414,
title = {Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates},
author = {Tang, Wan Si and Dimitrievska, Mirjana and Stavila, Vitalie and Zhou, Wei and Wu, Hui and Talin, A. Alec and Udovic, Terrence J.},
abstractNote = {The salt compounds NaB11H14, Na-7-CB10H13, Li-7-CB10H13, Na-7,8-C2B9H12, and Na-7,9-C2B9H12 all contain geometrically similar, monocharged, nido-undeca(carba)borate anions (i.e., truncated icosohedral-shaped clusters constructed of only 11 instead of 12 {B-H} + {C-H} vertices and an additional number of compensating bridging and/or terminal H atoms). We used first-principles calculations, X-ray powder diffraction, differential scanning calorimetry, neutron vibrational spectroscopy, neutron elastic-scattering fixed-window scans, quasielastic neutron scattering, and electrochemical impedance measurements to investigate their structures, bonding potentials, phase-transition behaviors, anion orientational mobilities, and ionic conductivities compared to those of their closo-poly(carba)borate cousins. All exhibited order-disorder phase transitions somewhere between room temperature and 375 K. All disordered phases appear to possess highly reorientationally mobile anions (> ~1010 jumps s-1 above 300 K) and cation-vacancy-rich, close-packed or body-center-cubic-packed structures [like previously investigated closo-poly(carba)borates]. Moreover, all disordered phases display superionic conductivities but with generally somewhat lower values compared to those for the related sodium and lithium salts with similar monocharged 1-CB9H10- and CB11H12- closo-carbaborate anions. This study significantly expands the known toolkit of solid-state, poly(carba)borate-based salts capable of superionic conductivities and provides valuable insights into the effect of crystal lattice, unit cell volume, number of carbon atoms incorporated into the anion, and charge polarization on ionic conductivity.},
doi = {10.1021/acs.chemmater.7b04332},
journal = {Chemistry of Materials},
number = 24,
volume = 29,
place = {United States},
year = {2017},
month = {11}
}