Development of sulfide glass-ceramic electrolytes for all-solid-state lithium rechargeable batteries

Development of Li2S–P2S5-based glass-ceramic electrolytes is reviewed. Superionic crystals of Li7P3S11 and Li3.25P0.95S4 were precipitated from the Li2S–P2S5 glasses at the selected compositions. These high temperature or metastable phases enhanced conductivity of glass ceramics up to over 10−3 S cm−1 at room temperature. The original (or mother) glass electrolytes itself showed somewhat lower conductivity of 10−4 S cm−1 and have important role as a precursor for obtaining the superionic crystals, which were not synthesized by a conventional solid-state reaction. The substitution of P2O5 for P2S5 at the composition 70Li2S·30P2S5 (mol%) improved both conductivity and electrochemical stability of glass-ceramic electrolytes. The all-solid-state In/LiCoO2 cell using the 70Li2S·27P2S5·3P2O5 (mol%) glass-ceramic electrolyte showed initial capacity of 105 mAh g−1 (gram of LiCoO2) at the current density of 0.13 mA cm−2 and exhibited higher electrochemical performance than that using the 70Li2S·30P2S5 glass-ceramic electrolyte.