Study of ion dynamics of LiI·6H2O in the supercooled liquid state using NMR spectroscopy and ionic conductivity measurements

Abstract

Ion dynamics in the liquid and supercooled liquid state of LiI·6H2O were studied by nuclear magnetic resonance (NMR) spectroscopy and ionic conductivity measurements. The self-diffusion coefficients of the water molecules and lithium ions were measured by 1H and 7Li pulsed gradient spin echo NMR (PGSE-NMR). The temperature dependences of the DC ionic conductivity and diffusion coefficients of lithium ions and water molecules were well-fitted by the Vogel-Tamman-Fulcher (VTF) law, similar to those of the LiCl·RH2O system. The conductivity and lithium diffusion coefficients of the LiI·6H2O system were more than twice those of LiCl·7H2O in the supercooled liquid state below 200 K, which could be attributed to the larger size of the iodide anions than that of chloride anions. The temperature dependence of the correlation times calculated from NMR T1 relaxation deviated from the VTF law at low temperatures because of the local orientational fluctuation of the water molecules.