Caraterização Elétrica dos sistemas cerâmicos de La(2/3-X)Li3XTiO3 e Li2TiO3

Abstract

The complex impedance spectroscopy technique was used to perform the electrical characterization of two ceramic systems: Lithium Titanate Lanthanum - La (2/3-X) Li3XTiO3 (LLTO) and Lithium Titanate - Li2TiO3 (LTO). The study is done on two samples for each system, LLTO (La0.59Li0.24TiO3 and La0.56Li0.33TiO3) and LTO (milled and unground). LLT nanoparticle powders were obtained by high energy milling (MAE) and sintered by Spark Plasma Sintering (SPS). On the other hand, the LTO was subjected to high energy grinding to reduce particle size and sintered by the conventional sintering method. The electrical response of both systems (LLTO and LTO) was studied, with the differential of evaluating the electrical properties in each case. Complex impedance measurements were performed in the frequency range of 1 Hz to 10 MHz and in a temperature range from room temperature to 270 ° C. Three models were used for experimental data processing, the equivalent circuit model, the extended Jonscher universal law and the derivative method. By means of the three models, it was possible to obtain the conductivity of DC and to study the contributions to the total conductivity, grain and grain boundary of the LLTO. While the LTO was studied in the frequency range of 1 Hz to 1 MHz, in the temperature range of 25 ° C to 200 ° C. The effect of grinding on ionic conductivity was verified in the LTO system. The intrinsic conductivity of LLTO (x = 0.08) was in the order of 10E-5 to 10E-3 S / cm in the temperature range studied. For the LTO the intrinsic ionic conductivity was of the order of 10E-10 to 10E-7 S/cm. In addition, the Arrhenius equation allowed to determine the total activation energy (Ea) of each contribution of both the LLTO and the LTO. For La0.59Li0.24TiO3, Ea values ​​of 0.394, 0.393 and 0.208 eV were obtained for the total volume, grain and grain frontier, respectively. Indicating that for the LLTO system the conductive mechanism is determined by the mobility of Li + ions. For the LTO without and with milling, activation energy of the total sample of approximately 0.69 and 0.687 eV, respectively, was obtained. These values ​​are associated with a mechanism of conduction by simply ionized oxygen vacancies.