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Polyhydroborate-based salts of lithium and sodium have attracted much recent interest as promising solid-state electrolytes for energy-related applications. A member of this family, sodium dicarba- nido -undecahydroborate Na-7,9-C 2 B 9 H 12  exhibits superionic conductivity above its order-disorder phase transition temperature, ∼360 K. To investigate the dynamics of the anions and cations in this compound at the microscopic level, we have measured the  1 H and  23 Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates over the temperature range of 148–384 K. It has been found that the transition from the low- T  ordered to the high- T  disordered phase is accompanied by an abrupt, several-orders-of-magnitude acceleration of both the reorientational jump rate of the complex anions and the diffusive jump rate of Na +  cations. These results support the idea that reorientations of large [C 2 B 9 H 12 ] −  anions can facilitate cation diffusion and, thus, the ionic conductivity. The apparent activation energies for anion reorientations obtained from the  1 H spin-lattice relaxation data are 314 meV for the ordered phase and 272 meV for the disordered phase. The activation energies for Na +  diffusive jumps derived from the  23 Na spin-lattice relaxation data are 350 and 268 meV for the ordered and disordered phases, respectively.

Anion reorientations and cation diffusion in a carbon-substituted sodium nido -borate Na-7,9-C 2 B 9 H 12 : 1 H and 23 Na NMR studies