Air‐Stable Li2S Cathodes Enabled by an In Situ‐Formed Li+ Conductor for Graphite‐Li2S Pouch Cells

Using Li2S cathodes instead of S cathodes presents an opportunity to pair them with Li‐free anodes (e.g., graphite), thereby circumventing anode‐related issues, such as poor reversibility and safety, encountered in Li‐S batteries. However, the moisture‐sensitive nature of Li2S causes the release of hazardous H2S and the formation of insulative by‐products, increasing the manufacturing difficulty and adversely affecting cathode performance. Here, Li4SnS4, a Li+ conductor that is air‐stable according to the hard–soft acid–base principle, is formed in situ and uniformly on Li2S particles because Li2S itself participates in Li4SnS4 formation. When exposed to air (20% relative humidity), the protective Li4SnS4 layer maintains its components and structure, thus contributing to the enhanced stability of the Li2S@Li4SnS4 composite. In addition, the Li4SnS4 layer can accelerate the sluggish conversion of Li2S because of its favorable interfacial charge transfer, and continuously confine lithium polysulfides owing to its integrity during electrochemical processes. A graphite‐Li2S pouch cell containing a Li2S@Li4SnS4 cathode is constructed, which shows stable cyclability with 97% capacity retention after 100 cycles. Hence, combining a desirable air‐stable Li2S cathode and a highly reversible Li‐free configuration offers potential practical applications of graphite‐Li2S full cells. An in situ formed Li+ conductor (Li4SnS4) layer is directly constructed on commercial Li2S particles to obtain air‐stable, shuttle‐free, and fast‐redox Li2S cathodes for graphite‐Li2S batteries.