RESUMEN
Coating the surface of the cathode active material of all-solid-state batteries with sulfide-based solid electrolytes is key for improving and enhancing the battery performance. Although lithium niobate (LiNbO3) is one of the most representative coating materials, its low durability at a highly charged potential and high temperature is an impediment to the realization of high-performance all-solid-state batteries. In this study, we developed new hybrid coating materials consisting of lithium niobate (Li-Nb-O) and lithium phosphate (Li-P-O) and investigated the influence of the ratio of P/(Nb + P) on the durability performance. The cathode half-cells, using a sulfide-based solid electrolyte Li6PS5Cl/cathode active material, LiNi0.5Co0.2Mn0.3O2, coated with the new hybrid coating materials of LiPxNb1-xO3 (x = 0-1), were exposed to harsh conditions (60 °C and 4.55 V vs Li/Li+) for 120 h as a degradation test. P substitution resulted in higher durability and lower interfacial resistance. In particular, the hybrid coating with x = 0.5 performed better, in terms of capacity retention and interfacial resistance, than those with other compositions of niobate and phosphate. The coated cathode active materials were analyzed using various analytical techniques such as scanning electron microscopy/energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XAS) to elucidate the improvement mechanism. Moreover, the degraded cathodes were observed using time-of-flight secondary-ion mass spectrometry, TEM/electron diffraction, and XAS. These analyses revealed that the Nb-O-P coordination in the hybrid coating material captured O by P. The coordination suppressed the release of O from the coating layer as a decomposition side reaction to realize a higher durability than that of LiNbO3.
RESUMEN
We have started the construction of a nationwide forensic soil sediment database for Japan based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points all over Japan obtained by high-resolution synchrotron X-ray powder diffraction (SR-XRD) and high-energy synchrotron X-ray fluorescence analysis (HE-SR-XRF). In this study, the performance of both techniques was demonstrated by analyzing soil sediments from two different geological regions, the Kofu and Chiba regions in Kanto province, to construct database that can be applied in the future to provenance analysis of soil evidence from a crime scene. The sediments from the quaternary volcanic lithology of the Chiba region were found to be dominated by heavy minerals of volcanic origin - orthopyroxene, clinopyroxene, and amphibole, and the REEs (rare earth elements) within the region showed similar geochemical behavior. On the other hand, four distinct heavy mineral groups were identified in the sediments of the Kofu region, where there is a great variety of underlying bedrock, and the geochemical behavior of the REEs in the sediments also varied accordingly to their geological origins. As such, our study shows that high-resolution SR-XRD data can provide information on the spatial distribution patterns of heavy minerals in stream sediments, playing an important role in determining their likely geographical origin. Meanwhile, the highly sensitive HE-SR-XRF data allow us to study the geochemical behavior of trace heavy elements, especially the REEs in the sediments, providing additional support to further constrain the likely geographical origin of the sediments determined by heavy minerals.