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  4. Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB11H12
 
research article

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

Dimitrievska, Mirjana  
•
Wu, Hui
•
Stavila, Vitalie
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August 20, 2020
Journal Of Physical Chemistry C

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 (P2(1)/c) and high-T disordered cubic (Fm (3) over barm) 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 x 10(6) s(-1) in the low-T phase (332 K) to 2.6 x 10(10) 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 x 10(-4 )S cm(-1 )at 361 K. However, this is still about 1 to 2 orders of magnitude lower than that observed for LiCB(11)H(12 )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.

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Type
research article
DOI
10.1021/acs.jpcc.0c05038
Web of Science ID

WOS:000563746200016

Author(s)
Dimitrievska, Mirjana  
Wu, Hui
Stavila, Vitalie
Babanova, Olga A.
Skoryunov, Roman, V
Soloninin, Alexei, V
Zhou, Wei
Trump, Benjamin A.
Andersson, Mikael S.
Skripov, Alexander, V
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Date Issued

2020-08-20

Publisher

AMER CHEMICAL SOC

Published in
Journal Of Physical Chemistry C
Volume

124

Issue

33

Start page

17992

End page

18002

Subjects

Chemistry, Physical

•

Nanoscience & Nanotechnology

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Materials Science, Multidisciplinary

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Chemistry

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Science & Technology - Other Topics

•

Materials Science

•

sodium superionic conduction

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nuclear-magnetic-resonance

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reorientational dynamics

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anion reorientations

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solid electrolytes

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neutron-scattering

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crystal-structures

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na

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cation

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a(2)b(12)h(12)

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
IMX  
Available on Infoscience
September 16, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/171695
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