To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO 4 ] À tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS).Lithium is the only mobile particle in these materials. Data derived from IS, i.e. activation energies, preexponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO 4 -LiAlSi 4 O 10 ) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol À1 ) are significantly lower than those in depolymerized networks (76 to 78 kJ mol À1 ) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.

In order to improve our understanding of the transport mechanisms of lithium in glasses, we have performed diffusion and ionic conductivity studies on spodumene composition (LiAlSi(2)O(6)) glasses. In diffusion couple experiments pairs of chemically identical glasses with different lithium isotopy (natural Li vs pure (7)Li) were processed at temperatures between 482 and 732 K. Profiles of lithium isotopes were measured after the diffusion runs innovatively applying femtosecond UV laser ablation combined with inductively coupled plasma mass spectrometry (LA ICP-MS). Self-diffusion coefficients of lithium in the glasses were determined by fitting the isotope profiles. During some of the diffusion experiments the electrical conductivity of the samples was intermittently measured by impedance spectrometry. Combining ionic conductivity and self-diffusivity yields a temperature-independent correlation factor of ~0.50, indicating that motions of Li ions are strongly correlated in this type of glasses. Lithium self-diffusivity in LiAlSi(2)O(6) glass was found to be very similar to that in lithium silicate glasses although Raman spectroscopy demonstrates structural differences between these glasses; that is, the aluminosilicate is completely polymerized while the lithium silicate glasses contain large fractions of nonbridging oxygen.

In order to better understand the mechanisms of lithium dynamics and to elucidate the influence of defects in lithium mobility, we have studied the Li-ion propagation through natural single crystals of α-spodumene, LiAlSi2O6 and petalite, LiAlSi4O10 using impedance spectroscopy. Electrical conductivity in petalite and α-spodumene is 4–5 orders of magnitude lower than in glasses of the same composition, and three orders of magnitude lower than in synthetic β-spodumene. Conductivity in α-spodumene is anisotropic with conductivity along the c-axis being 0.3–0.4 log units higher than perpendicular to the c-axis. Contrary to α-spodumene, isotropic conductivity was observed for petalite single crystals. Despite the large difference in conductivity values, the activation energies for ionic conduction of α-spodumene along the c-axis (74 to 86 kJ/mol) are only slightly higher than for LiAlSi2O6 and LiAlSi4O10 glasses (∼67 kJ/mol). On the other hand, much higher activation energies of 112–134 kJ/mol were determined for petalite. Based on our investigation, a vacancy-controlled transport mechanism is indicated for the densely packed α-spodumene structure, while in the open framework structure of petalite formation and movement of Li interstitials is proposed to be dominant mechanism for charge transfer.