Nuclear Magnetic Resonance
Studies of Reorientational Motion and Li Diffusion in LiBH<sub>4</sub>–LiI Solid Solutions
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Abstract
To study the reorientational motion of the BH<sub>4</sub> groups and the translational diffusion of Li<sup>+</sup> ions in
LiBH<sub>4</sub>–LiI solid solutions with 2:1, 1:1, and 1:2
molar ratios, we have measured the <sup>1</sup>H, <sup>11</sup>B,
and <sup>7</sup>Li NMR spectra and spin–lattice relaxation
rates in these compounds over the temperature range 18–520
K. It is found that, at low temperatures, the reorientational motion
of the BH<sub>4</sub> groups in LiBH<sub>4</sub>–LiI solid
solutions is considerably faster than in all other borohydride-based
systems studied so far. Our results are consistent with a coexistence
of at least two types of reorientational processes with different
characteristic rates. For the faster reorientational process, the
average activation energies derived from our data are 53 ± 4,
39 ± 4, and 33 ± 4 meV for the LiBH<sub>4</sub>–LiI
solid solutions with 2:1, 1:1, and 1:2 molar ratios, respectively.
In the studied range of iodine concentrations, the Li<sup>+</sup> jump
rates are found to decrease with increasing I<sup>–</sup> content.
The activation energies for Li diffusion obtained from our data are
0.63 ± 0.01, 0.65 ± 0.01, and 0.68 ± 0.01 eV for the
samples with 2:1, 1:1, and 1:2 molar ratios, respectively