Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 124, Issue 33, Pages 17992-18002Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.0c05038
Keywords
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Funding
- US DOE Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office [DE-AC3608GO28308]
- Swedish Research Council [2017-06345]
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA-0003525]
- Russian Science Foundation [19-12-00009]
- National Science Foundation [DMR-1508249]
- US DOE [DE-AC02-06CH11357]
- Swedish Research Council [2017-06345] Funding Source: Swedish Research Council
- Russian Science Foundation [19-12-00009] Funding Source: Russian Science Foundation
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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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