A Hundreds‐Milliampere‐Hour‐Scale Solid‐State Aluminum–Sulfur Pouch Cell

Abstract Aluminum‐sulfur (Al–S) batteries are exploited as an ideal power source for grid‐scale energy storage due to the abundant Al and S resources and superior safety. However, the short lifespan and lack of appropriate current collectors for positive electrodes have restricted the large‐size manufacture and practicability of Al–S batteries. Here a solid‐state electrolyte and current collector‐free positive electrode are demonstrated to construct a large‐size solid‐state Al–S pouch cell. The ionic liquid‐impregnated metal–organic‐framework solid electrolytes are filled into the gel polymer electrolyte to achieve the large‐size production of composite solid‐state electrolyte (MSE@GPE). Meanwhile, the MSE@GPE electrolytes, serving as the binder and ionic conductor, are introduced into sulfur‐anchored cobalt/nitrogen co‐doped graphene to prepare an all‐in‐one composite sulfur‐positive electrode without a current collector. The as‐assembled Al–S pouch cell delivers a reversible capacity of 288 mAh and a cell‐level energy density of >90 Wh kg −1 . Furthermore, the cycle life of this Al–S pouch cell can reach over 400 times with capacity retention of 80%, benefiting from the significant inhibiting effect of MSE@GPE electrolyte on the shuttle effect of polysulfide. The results provide a path for fabricating practical Al–S batteries, narrowing the gap between their high theoretical specific energy and the realization in practical operation.