Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and...

Realization of all-solid-state batteries combined with metallic Li/Na is still hindered due to the unstable interface between the alkali metal and solid electrolytes, especially for highly promising thiophosphate materials. Artificial and uniform solid-electrolyte interphases (SEIs), serving as thin ion-conducting films, have been considered as a strategy to overcome the issues of such reactive interfaces. Here, we synthesized sulfide-based artificial SEIs (LiS and NaS) on Li and Na by solid/gas reaction between the alkali metal and S vapor. The synthesized films are carefully characterized with various chemical/electrochemical techniques. We show that these artificial SEIs are not beneficial from an application point of view since they either contribute to additional resistances (Li) or do not prevent reactions at the alkali metal/electrolyte interface (Na). We show that NaS is more porous than LiS, supported by (i) its rough morphology observed by focused ion beam-scanning electron microscopy, (ii) the rapid decrease of R_interface (interfacial resistance) in NaS-covered-Na symmetric cells with liquid electrolyte upon aging under open-circuit potential, and (iii) the increase of R_interface in NaS-covered-Na solid-state symmetric cells with Na₃PS₄ electrolyte. The porous SEI allows the penetration of liquid electrolyte or alkali metal creep through its pores, resulting in a continuous chemical reaction. Hence, porosity of SEIs in general should be carefully taken into account in the application of batteries containing both liquid electrolyte and solid electrolyte.