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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)
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