Solid state lithiation–delithiation of sulphur in sub-nano confinement: a new concept for designing lithium–sulphur batteries

We investigate the detailed effects and mechanisms of sub-nano confinement on lithium–sulfur (Li–S) electrochemical reactions in both ether-based and carbonate-based electrolytes. Our results demonstrate a clear correlation between the size of sulfur confinement and the resulting Li–S electrochemical mechanisms. In particular, when sulfur is confined within sub-nano pores, we observe identical lithium–sulfur electrochemical behavior, which is distinctly different from conventional Li–S reactions, in both ether and carbonate electrolytes. Taken together, our results highlight the critical importance of sub-nano confinement effects on controlling solid-state reactions in Li–S electrochemical systems.