Enhancing the Interfacial Stability of the Li2S–SiS2–P2S5 Solid Electrolyte toward Metallic Lithium Anode by LiI Incorporation

Chalcogenide solid-state electrolytes (SEs) have been regarded as promising candidates for lithium dendrite suppression due to their high ionic conductivity, suitable mechanical strength, and large Li+ ion transference number. However, the wide applications of SEs in pragmatic all-solid-state batteries are still retarded by their limited interface stability, which leads to lithium dendrite growth and formation of interphase with high resistance. In addition, the interphase evolution mechanism between SEs and metallic Li anodes remains unclear. Herein, this work demonstrates that the interfacial stability of Li2S-SiS2-P2S5 SEs can be effectively enhanced by tuning the interphase through LiI incorporation. This strategy contributes to a high ionic conductivity of the SEs and electronic insulation interphase containing LiI. Thus, the 70(60Li2S-28SiS2-12P2S5)-30 LiI SEs prepared by melt-quenching exhibit a high ionic conductivity of 1.74 mS cm-1 at room temperature and a larger critical current density of 1.65 mA cm-2 at 65 °C. The cycling life of the symmetric Li|SEs|Li cell is up to 200 h without significant resistance growth at 0.1 mA cm-2 at room temperature. This enhanced interface stability is revealed to originate from the in situ-formed LiI within the interphase, which prevents continual SEs degradation and suppresses lithium dendrite growth. This work provides a vital understanding of interphase evolution, which is valuable for designing SEs with long cycling stability.