Li₂S-Based Composite Cathode with in Situ-Generated Li₃PS₄ Electrolyte on Li₂S for Advanced All-Solid-State...

All-solid-state lithium-sulfur batteries (ASSLSBs) are considered to be a promising solution for the next generation of energy storage systems due to their high theoretical energy density and improved safety. However, the practical application of ASSLSBs is hindered by several critical challenges, including the poor electrode/electrolyte interface, sluggish electrochemical kinetics of solid-solid conversion between S and Li₂S in the cathode, and big volume changes during cycling. Herein, the 85(92Li₂S-8P₂S₅)-15AB composite cathode featuring an integrated structure of a Li₂S active material and Li₃PS₄ solid electrolyte is developed by in situ generating a Li₃PS₄ glassy electrolyte on Li₂S active materials, resulting from a reaction between Li₂S and P₂S₅. The well-established composite cathode structure with an enhanced electrode/electrolyte interfacial contact and highly efficient ion/electron transport networks enables a significant enhancement of redox kinetics and an areal Li₂S loading for ASSLSBs. The 85(92Li₂S-8P₂S₅)-15AB composite demonstrates superior electrochemical performance, exhibiting 98% high utilization of Li₂S (1141.7 mAh g_(Li2S)^-1) with both a high Li₂S active material content of 44 wt % and corresponding areal loading of 6 mg cm^-2. Moreover, the excellent electrochemical activity can be maintained even at an ultrahigh areal Li₂S loading of 12 mg cm^-2 with a high reversible capacity of 880.3 mAh g^-1, corresponding to an areal capacity of 10.6 mAh cm^-2. This study provides a simple and facile strategy to a rational design for the composite cathode structure achieving fast Li-S reaction kinetics for high-performance ASSLSBs.