Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

Abstract The hexagonal mixed-anion solid solution Na 2 (CB 9 H 10 )(CB 11 H 12 ) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1 H and 23 Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na 2 (CB 9 H 10 )(CB 11 H 12 ) over the temperature range of 80–435 K. It is found that the diffusive motion of Na + ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na + jump process is characterized by the activation energy of 353(11) meV. Although Na + mobility in Na 2 (CB 9 H 10 )(CB 11 H 12 ) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na + jumps should be taken into account. The measured 1 H spin-lattice relaxation rates for Na 2 (CB 9 H 10 )(CB 11 H 12 ) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, both reorientational processes are found to be faster than the Na + jump process responsible for the long-range diffusion.