Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries

“Quasi-solid-state” conversion mechanisms using sparingly solvating electrolytes (SPSEs) bridge the gap between traditional solid–liquid–solid and solid-state sulfur conversion in lithium–sulfur (Li–S) batteries. Although these terms are commonly used, their precise distinctions and impacts on key performance metrics, such as rate capability, energy density, and capacity fading, remain poorly understood. In this work, we employ operando small- and wide-angle X-ray scattering alongside cryogenic transmission electron microscopy (cryo-TEM) to compare Li–S batteries in sparingly solvating and solvating ether-based electrolytes. We find that, unlike solvating electrolytes, SPSEs lead to an extended presence of lithium sulfide during cycling, coexisting with sulfur at a 50% state of charge and beyond. In the charged state, solid sulfur is present in its amorphous form inside the carbon black nanopores. These findings indicate that the limited solubility confines polysulfides in regions near the carbon surface, where these polysulfides enable conversion between the coexisting solid discharge and charge product.