Design of Cathode Coating Using Niobate and Phosphate Hybrid Material for Sulfide-Based Solid-State Battery

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, LiNi_0.5Co_0.2Mn_0.3O₂, coated with the new hybrid coating materials of LiPNb_1-O₃ (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.