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Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB11H12

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [4];  [4];  [2];  [2];  [5];  [4];  [6]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; National Renewable Energy Lab. (NREL), Golden, CO (United States); Ecole Polytechnique Federale Lausanne (Switzerland)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  4. Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation)
  5. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Chalmers University of Technology, Göteborg (Sweden)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Maryland, College Park, MD (United States)
+ Show Author Affiliations

MCB11H12 (M: Li, Na) dodecahydro-monocarba-closo-dodecaborate salt compounds are known to have stellar superionic Li+ and Na+ conductivities in their high-temperature disordered phases, making them potentially appealing electrolytes in all-solid-state batteries. Nonetheless, it is of keen interest to search for other related materials with similar conductivities while at the same time exhibiting even lower (more device-relevant) disordering temperatures, a key challenge for this class of materials. With this in mind, the unknown structural and dynamical properties of the heavier KCB11H12 congener were investigated in detail by X-ray powder diffraction, differential scanning calorimetry, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and AC impedance measurements. This salt indeed undergoes an entropy-driven, reversible, order–disorder transformation and with a lower onset temperature (348 K upon heating and 340 K upon cooling) in comparison to the lighter LiCB11H12 and NaCB11H12 analogues. The K+ cations in both the low-T ordered monoclinic (P21/c) and high-T disordered cubic ($$Fm\bar{3}m$$) structures occupy octahedral interstices formed by CB11H12– anions. In the low-T structure, the anions orient themselves so as to avoid close proximity between their highly electropositive C–H vertices and the neighboring K+ cations. In the high-T structure, the anions are orientationally disordered, although to best avoid the K+ cations, the anions likely orient themselves so that their C–H axes are aligned in one of eight possible directions along the body diagonals of the cubic unit cell. Across the transition, anion reorientational jump rates change from 6.2 × 106 s–1 in the low-T phase (332 K) to 2.6 × 1010 s–1 in the high-T phase (341 K). In tandem, K+ conductivity increases by about 30-fold across the transition, yielding a high-T phase value of 3.2 × 10–4 S cm–1 at 361 K. However, this is still about 1 to 2 orders of magnitude lower than that observed for LiCB11H12 and NaCB11H12, suggesting that the relatively larger K+ cation is much more sterically hindered than Li+ and Na+ from diffusing through the anion lattice via the network of smaller interstitial sites.

Research Organization:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1783768
Alternate ID(s):
OSTI ID: 1659298
OSTI ID: 1677489
Report Number(s):
SAND--2021-5797J; 696165
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 33 Vol. 124; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Cations
Chemical structure
Phase transitions
Potassium