Chloride‐Reinforced Carbon Nanofiber Host as Effective Polysulfide Traps in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) battery is one of the most promising alternatives for the current state‐of‐the‐art lithium‐ion batteries due to its high theoretical energy density and low production cost from the use of sulfur. However, the commercialization of Li–S batteries has been so far limited to the cyclability and the retention of active sulfur materials. Using co‐electrospinning and physical vapor deposition procedures, we created a class of chloride–carbon nanofiber composites, and studied their effectiveness on polysulfides sequestration. By trapping sulfur reduction products in the modified cathode through both chemical and physical confinements, these chloride‐coated cathodes are shown to remarkably suppress the polysulfide dissolution and shuttling between lithium and sulfur electrodes. From adsorption experiments and theoretical calculations, it is shown that not only the sulfide‐adsorption effect but also the diffusivity in the vicinity of these chlorides materials plays an important role on the reversibility of sulfur‐based cathode upon repeated cycles. Balancing the adsorption and diffusion effects of these nonconductive materials could lead to the enhanced cycling performance of an Li–S cell. Electrochemical analyses over hundreds of cycles indicate that cells containing indium chloride‐modified carbon nanofiber outperform cells with other halogenated salts, delivering an average specific capacity of above 1200 mAh g(−1) at 0.2 C.