Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography

Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behaviour and stability at solid–solid interfaces remains limited compared to at solid–liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth and volumetric changes determines cell behaviour. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur owing to partial molar volume mismatches at either electrode. These results provide insight into how chemo-mechanical phenomena can affect cell performance, thus facilitating the development of solid-state batteries. Understanding electrochemical behaviour and stability at solid–solid interfaces remains challenging. Operando synchrotron X-ray computed microtomography loss reveals that reconfiguration of interfacial contact is critical to explain cell failure during solid-state battery cycling.