Synergistic Interface Stability and High Room-Temperature Ionic Conductivity for Wide-Temperature All-Solid-State Batteries Based on Li6+xSixSb1-xS5I Electrolytes

Abstract

Solid-state lithium-ion batteries (LIBs) are increasingly recognized for their exceptional energy density and safety. However, their widespread adoption is challenged by persistent issues such as thermal and electrochemical instability, dendrite formation, and limited compatibility with high-voltage cathodes. Sulfide-based solid electrolytes (SEs), particularly iodide argyrodites, offer outstanding ionic conductivity and stability; however, their practical application is constrained by the formation of space-charge layers, slow ion transport, and susceptibility to dendrite penetration. To address these challenges, we synthesized a novel Li6.6Si0.6Sb0.4S5I argyrodite electrolyte via ball milling and heat treatment, achieving a remarkable room-temperature ionic conductivity of 9.9 mS cm^-1. The electrolyte was integrated with a LiNbO3-coated LiNi0.7Co0.1Mn0.2O2 cathode to form an all-solid-state battery, which demonstrated an initial discharge capacity of 171.2 mAh g^-1, retained 84.2% of its capacity after 200 cycles at 0.5C, and maintained stable cycling across a broad temperature range from -20 degrees C to 60 degrees C. Our study shows that tailored electrolyte composition and a composite cathode configuration significantly enhance cycling stability and improve interfacial protection. These findings highlight the potential of Si-doped antimony-type iodide argyrodites for next-generation high-performance all-solid-state batteries, offering durable operation under diverse thermal conditions.