Insulator:conductor interfacial regions - Li ion dynamics in the nanocrystalline dispersed ionic conductor LiF:TiO2

Lithium fluoride is known to be a very poor ionic conductor. Here, we used it as a model substance to investigate the influence of the insulator TiO2 on ion dynamics in nanocrystalline composites of LiF and TiO2. In such two-phase systems a percolation network of fast Li+ pathways at the conductor:insulator interfaces may lead to enhanced overall, through-going ionic (and electronic) transport. Indeed, we observed such an effect and characterized it by conductivity spectroscopy as well as by variable-temperature Li-7 and F-19 Nuclear Magnetic Resonance (NMR) line shape measurements and diffusion-induced NMR relaxometry. Compared to nanocrystalline LiF, a remarkable increase in total conductivity of almost four orders of magnitude, that is, from 6x10(-11) S cm(-1) up to 2x10(-7) S cm(-1) (100 degrees C) was observed for LiF:TiO2 containing 40 vol.-% of TiO2. Direct current polarization measurements revealed that principally ionic charge carriers are responsible for this enhancement. As both ions in LiF, Li+ and F-, might be mobile, NMR helped revealing that Li+ is the charge carrier being mainly responsible for the increase in ionic conductivity. Compared to SiO2 and Al2O3 [see, S. Breuer et al. J. Phys. Chem. C, 2019, 123, 5222], with TiO2 the largest increase in conductivity was achieved. Hence the introduction of heterogeneous conductor:insulator contacts turned out to be a highly suitable tool to effectively engineer the interfacial regions in such two-phase systems. In general, such a composite effect is important for ion transport in components for energy storage devices and in the solid electrolyte interphase region that generally passivates the anode material in lithium-ion batteries.

Automated summary

The study shows that in nanocrystalline composites of LiF and TiO2, TiO2 leads to significant changes in ion dynamics, resulting in a remarkable increase in overall conductivity. NMR experiments revealed that Li+ is the primary charge carrier responsible for the increase in ionic conductivity. Therefore, the introduction of heterogeneous conductor:insulator contacts is an effective tool for engineering the interfacial regions in such two-phase systems.