A Molecular‐Cage Strategy Enabling Efficient Chemisorption–Electrocatalytic Interface in Nanostructured Li 2 S Cathode for Li Metal‐Free Rechargeable Cells with High Energy

Using high‐capacity and metallic Li‐free lithium sulfide (Li 2 S) cathodes offers an alternative solution to address serious safety risks and performance decay caused by uncontrolled dendrite hazards of Li metal anodes in next‐generation Li metal batteries. Practical applications of such a cathode, however, still suffer from low redox activity, unaffordable cost, and poor processability of infusible and moisture‐sensitive Li 2 S. Herein, these difficulties are addressed by developing a molecular cage–engaged strategy that enables low‐cost production and interfacial engineering of Li 2 S cathodes for rechargeable Li 2 S//Si cells. An efficient chemisorption–electrocatalytic interface is built in extremely nanostructured Li 2 S cathodes by harnessing the confinement/separation effect of metal–organic molecular cages on ionic clusters of air‐stable, soluble, and low‐cost Li salt and their chemical transformation. It effectively boosts the redox activity toward Li 2 S activation/dissociation and polysulfide chemisorption–conversion in Li‐S batteries, leading to low activation voltage barrier, stable cycle life of 1000 cycles, ultrafast current rate up to 8 C, and high areal capacities of Li 2 S cathodes with high mass loading. Encouragingly, this highly active Li 2 S cathode can be applied for constructing truly workable Li 2 S//Si cells with a high specific energy of 673 Wh kg −1 and stable performance for 200 cycles at high rates against hollow nanostructured Si anode.