Design of Solid Polycationic Electrolyte to Enable Durable Chloride‐Ion Batteries

The high energy density and cost‐effectiveness of chloride‐ion batteries (CIBs) make them promising alternatives to lithium‐ion batteries. However, the development of CIBs is greatly restricted by the lack of compatible electrolytes to support cost‐effective anodes. Herein, we present a rationally designed solid polycationic electrolyte (SPE) to enable room‐temperature chloride‐ion batteries utilizing aluminum (Al) metal as an anode. This SPE endows the CIB configuration with improved air stability and safety (i.e. free of flammability and liquid leakage). A high ionic conductivity (1.3×10−2 S cm−1 at 25 °C) has been achieved by the well‐tailored solvation structure of the SPE. Meanwhile, the solid polycationic electrolyte ensures stable electrodes|electrolyte interfaces, which effectively inhibit the growth of dendrites on the Al anodes and degradation of the FeOCl cathodes. The Al|SPE|FeOCl chloride‐ion batteries showcased a high discharge capacity around 250 mAh g−1 (based on the cathodes) and extended lifespan. Our electrolyte design opens a new avenue for developing low‐cost chloride‐ion batteries.