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

Abstract

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) in comparison to the lighter LiCB11H12 and NaCB11H12 analogues. The K+ cations in both the low- ordered monoclinic ( ) and high- disordered cubic (Fm-3m) structures occupy octahedral interstices formed by the anions. In the low- 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- 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- phase (332 K) to 2.6×1010 s-1 in the high- phase (341 K). In tandem, K+ conductivity increases by about thirty-fold across the transition, yielding a high- phase value of 3.2×10-4 S cm-1 at 361 K. Yet, this is still about one to two 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.