Transport and Electrochemical Properties of Li4Ti5O12-Li2TiO3 and Li4Ti5O12-TiO2 Composites

The study demonstrates that the introduction of the electrochemically inactive dielectric additive Li₂TiO₃ to LTO results in a strong decrease in the grain boundary resistance of LTO-Li₂TiO₃ (LTC) composites at a low concentration of Li₂TiO₃. With the increase in the concentration of Li₂TiO₃ in LTC composites, the grain boundary resistance goes through a minimum and increases again due to the growth of the insulation layer of small Li₂TiO₃ particles around LTO grains. For LTO-TiO₂ (LTT) composites, a similar effect was observed, albeit not as strong. It was found that LTC composites at low concentration of Li₂TiO₃ have unusually high charge–discharge capacity exceeding the theoretical value for pure LTO. This effect is likely to be caused by the occurrence of the electrochemical activity of Li₂TiO₃ in the vicinity of the interfaces between LTO and Li₂TiO₃. The increase in the capacity may be qualitatively described in terms of the model of two-phase composite in which there is the interface layer with a high capacity. Contrasting with LTC composites, in LTT composites, no capacity enhancement was observed, which was likely due to a noticeable difference in crystal structures of LTO and TiO₂ preventing the formation of coherent interfaces.