Mitigation of grain boundary resistance in La2/3-xLi3xTiO3 perovskite as an electrolyte for solid-state Li-ion batteries
Tomasz Polczyk, Wojciech Zając, Magdalena Ziąbka, Konrad Świerczek
Abstract
Abstract In this work, we report that modification of the chemical composition of grain boundaries of La 2/3-x Li 3x TiO 3 double perovskite, one of the most promising Li-ion conducting solid electrolytes, can be a convenient and versatile way of controlling the space charge potential, leading to a mitigated electrical resistance of the grain boundaries. Two groups of additives are investigated: lithium-enriching agents (Li 3 BO 3 , LiF) and 3 d metal ions (Co 2+ , Cu 2+ ), both expected to reduce the Schottky barrier. It is observed that Li-containing additives work effectively at a higher sintering temperature of 1250 °C. Regarding copper, it shows a much stronger positive impact at lower temperature, 1150 °C, while the addition of cobalt is always detrimental. Despite overall complex behavior, it is documented that the decreased space charge potential plays a more important role in the improvement of lithium conduction than the thickness of the grain boundaries. Among the proposed additives, modification of La 2/3-x Li 3x TiO 3 by 2 mol.% Cu 2+ results in the space charge potential reduction by 32 mV in relation to the reference sample, and the grain boundary specific conductivity increase by 80%, as measured at 30 °C. Introduced additive allows to obtain a similar effect on the conductivity as elevating the sintering temperature, which can facilitate manufacturing procedure. Graphic abstract