Ordered and Expanded Li Ion Channels for Dendrite‐Free and Fast Kinetics Lithium–Sulfur Battery

The uncontrolled polysulfide shuttling and lithium dendrite growth greatly impede the practical implementation of Li–S batteries. These issues can be alleviated by constructing an artificial layer that immobilizes soluble polysulfides and regulates Li+ flux. Here, a layer‐expanded lithium montmorillonite is fabricated through molecular intercalation to serve as a dual regulator for Li–S batteries. The lithiophilic montmorillonite, with its ordered and expanded Li+ diffusion channels, exhibits a high transference number, and promotes homogeneous Li deposition. Additionally, its moderate adsorption of polysulfides, combined with favorable Li diffusion behavior, enhanced the redox kinetics of sulfur species. This unique structure enables a prolonged lifespan of 1000 cycles at 0.5C with a low capacity decay of 0.04% per cycle for practical Li–S batteries.