A Dual Anion Chemistry‐Based Superionic Glass Enabling Long‐Cycling All‐Solid‐State Sodium‐Ion Batteries

Abstract Glassy Na‐ion solid‐state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state‐of‐the‐art GNSSEs at room temperature lessens their promise in the development of all‐solid‐state Na‐ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na2O2‐TaCl5 (NTOC), based on dual‐anion sublattice of oxychlorides. The unique local structures with abundant bridging and non‐bridging oxygen atoms contributes to a highly disordered Na‐ion distribution as well as low Na+ migration barrier within NTOC, enabling an ultrahigh ionic conductivity of 4.62 mS cm−1 at 25 °C (more than 20 times higher than those of previously reported GNSSEs). Moreover, the excellent formability of glassy NTOC electrolyte and its high electrochemical oxidative stability ensure a favourable electrolyte‐electrode interface, contributing to superior cycling stability of ASSNIBs for over 500 cycles at room temperature. The discovery of glassy NTOC electrolyte would reignite research enthusiasm in superionic glassy SSEs based on multi‐anion chemistry.