Lithium ion diffusion in Li beta-alumina single crystals measured by pulsed field gradient NMR spectroscopy

作者：Chowdhury Mohammed Tareque^*; Takekawa Reiji; Iwai Yoshiki; Kuwata Naoaki; Kawamura Junichi

来源：Journal of Chemical Physics, 2014, 140(12): 124509.

DOI：10.1063/1.4869347

The lithium ion diffusion coefficient of a 93% Li beta-alumina single crystal was measured for the first time using pulsed field gradient (PFG) NMR spectroscopy with two different crystal orientations. The diffusion coefficient was found to be 1.2 x 10(-11) m(2)/ s in the direction perpendicular to the c axis at room temperature. The Li ion diffusion coefficient along the c axis direction was found to be very small (6.4 x 10(-13) m(2)/ s at 333 K), which suggests that the macroscopic diffusion of the Li ion in the beta-alumina crystal is mainly two- dimensional. The diffusion coefficient for the same sample was also estimated using NMR line narrowing data and impedance measurements. The impedance data show reasonable agreement with PFG-NMR data, while the line narrowing measurements provided a lower value for the diffusion coefficient. Line narrowing measurements also provided a relatively low value for the activation energy and pre- exponential factor. The temperature dependent diffusion coefficient was obtained in the temperature range 297-333 K by PFG-NMR, from which the activation energy for diffusion of the Li ion was estimated. The activation energy obtained by PFG-NMR was smaller than that obtained by impedance measurements, which suggests that thermally activated defect formation energy exists for 93% Li beta-alumina single crystals. The diffusion time dependence of the diffusion coefficient was observed for the Li ion in the 93% Li beta-alumina single crystal by means of PFG-NMR experiments. Motion of Li ion in fractal dimension might be a possible explanation for the observed diffusion time dependence of the diffusion coefficient in the 93% Li beta-alumina system.

• 出版日期2014-3-28