Study of the Cathode/Electrolyte Interface in an All-Sulfide-Solid-State Battery Using Lithium-Rich Transition Metal Sulfide

All-solid-state lithium batteries (ASSBs) are among the most promising energy storage technologies, particularly for electric vehicles, due to their enhanced safety. However, performances of these systems are still hindered by interfacial side reactions at electrode/electrolyte interfaces, especially when sulfide electrolytes are used, and additional issues of mechanical nature. In this work, an ASSB system composed of an argyrodite (Li_5.7PS_4.7Cl_1.3) electrolyte, a lithium-rich sulfide cathode (Li_1.2Ti_0.8S₂) operating at moderate voltage, and a lithium metal anode is investigated. The positive electrode/electrolyte interface is scrutinized during several battery cycles using X-ray photoelectron spectroscopy (XPS) via two complementary approaches (ex situ and in situ). We show that both titanium and sulfur species contribute to the electrochemical process without any detectable degradation of the electrolyte after 20 cycles and without the use of any protective coating. These results suggest that the electrochemical performances of such an all-sulfide system are not limited by the cathode/electrolyte reactivity, opening a promising route for the development of specific cathode materials adapted to sulfide electrolytes.