Synthesis and Electrochemical Performance of Lithium Lanthanum Titanate Solid-state Electrolyte

Abstract

With the increasing demand for large electronic devices, such as electric vehicle (EV), hybrid vehicles (HEV), energy storage devices have become more prominent. Lithium-ion rechargeable batteries have been one of the most popular vital topics in this area. For developing the next generation lithium-ion batteries with higher energy capacity and safety, solid-state electrolytes play an important role in improving ionic conductivity and preventing leakage in lithium-ion batteries. Lithium lanthanum titanate (Li3xLa2/3–xTiO3, LLTO) is a ceramic oxide solid-state electrolyte material, which has attracted many interests due to its high chemical stability, wide voltage window and high ionic conductivity (10-3 S/cm). However poor grain boundary conductivity of LLTO and electrode/electrolyte inter-facial problem limit the overall ionic conductivity and rate capacity of LLTO based solid battery systems. Therefore, optimizing the grain boundary conductivity, minimizing the interface issues and increasing the total conductivity of LLTO solid-state electrolytes are imminent. In this thesis, three approaches for enhancing ionic conductivity of LLTO based materials were developed: spark plasma sintering technology, oxygen vacancy manipulation and SiO2 doping. Spark plasma sintering technology enhances the processing methodology of LLTO to prevent lithium-ions loss at grain boundary, thus improving the grain boundary conductivity of LLTO to 1.624×10-6 S/cm. Oxygen vacancy manipulation uses post-annealing procedures to tailor oxygen levels of LLTO, which influenced the crystal structure and changed lithium-ions conduction mechanism of LLTO, resulting an enhanced overall ionic conductivity to 3.38×10-5 S/cm. SiO2 doping process creates the amorphous layers at grain boundary of LLTO to minimize the grain boundary resistance effect, thereby further improving the grain boundary conductivity to 1.96×10-4 S/cm. The purpose of this study is to understand Lithium-ions migration mechanism and optimize the electrochemical performance of LLTO solid-state electrolyte.