Self-diffusion of lithium, hydrogen, and oxygen ions in crystalline lithium hydroxide

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The self-diffusion coefficients of ions of the three chemical elements forming lithium hydroxide have been determined by the crystal-crystal and crystal-gas isotope exchange method in the temperature range 500–720 K. Crystal samples with different isotope compositions have been grown by the Bridgman method from melts. The melting temperature is 743 ± 2 K. Original methods have been developed for high-precision measurements of the isotope ratios of all three elements, i.e., lithium (6Li/7Li), hydrogen (H/D), and oxygen (16O/18O), and their changes after diffusion annealings with the use of the same sample. The self-diffusion coefficients of lithium and hydrogen ions differ but by a factor of no more than 3–5; however, their values exceed those for oxygen by several orders of magnitude. In particular, at 670 K, they are equal to 6.0 × 10−9, 3.2 × 10−9, and 2.0 × 10−12 cm2 s−1 for hydrogen, lithium, and oxygen, respectively. In the range 680–720 K, the self-diffusion coefficients of hydrogen and lithium increase sharply with increasing temperature to approximately 10−6 cm2 s−1. A probable mechanism of migration of protons and lithium ions in LiOH and the role played in this process by the oxygen ions with a lower mobility have been discussed.