Journal of the American Ceramic Society, Vol.101, No.1, 347-355, 2018
Thermal regimes of Li-ion conductivity in beta-eucryptite
While it is well-established that ionic conduction in lithium aluminosilicates proceeds via hopping of Li ions, the nature of the various hoping-based mechanisms in different temperature regimes has not been fully elucidated. The difficulties associated with investigating the conduction have to do with the presence of grains and grain boundaries of different orientations in these usually polycrystalline materials. Herein, we use electrochemical impedance spectroscopy (EIS) to investigate the ion conduction mechanisms in beta-eucryptite, which is a prototypical lithium aluminosilicate. In the absence of significant structural transitions in grain boundaries, we find that there are three conduction regimes for the one-dimensional ionic motion along the c axis channels in the grains, and determine the activation energies for each of these temperature regimes. Activation energies computed from molecular statics calculations of the potential energy landscape encountered by Li ions suggest that at temperatures below 440 degrees C conduction proceeds via cooperative or correlated motion, in agreement with established literature. Between 440 degrees C and 500 degrees C, the activation barriers extracted from EIS measurements are large and consistent with those from atomistic calculations for uncorrelated Li ion hopping. Above 500 degrees C the activation barriers decrease significantly, which indicates that after the transition to the Li-disordered phase of beta-eucryptite, the Li ion motion largely regains the correlated character.