Enhanced Polysulfide Redox Reaction of Co/Fe Dual‐Atom Catalysts Embedded in Metal–Organic Framework–Derived Microporous Carbon Electrode for Lithium–Sulfur Cells

ABSTRACT Lithium–sulfur (Li–S) batteries have attracted significant interest owing to their high theoretical energy densities and cost‐effectiveness. However, their practical application is hindered by sluggish lithium polysulfide (LiPS) redox kinetics and the shuttle effect, which result in rapid capacity decay and poor rate performance. Herein, a Co–Fe dual‐atom catalyst embedded in nitrogen‐doped microporous carbon (CoFeDA‐CN) is rationally designed to address these limitations. In CoFeDA‐CN, the spatially adjacent Co and Fe atomic centers are stabilized by nitrogen coordination within the MOF‐derived porous carbon matrix, providing a strong chemical affinity for LiPSs and promoting efficient redox conversion. The dual‐metal synergy effectively modulates the electronic structure at the active sites, thereby facilitating reversible conversion between long‐chain polysulfides and Li ₂ S, while effectively suppressing polysulfide dissolution. As a result, the CoFeDA‐CN@S cathode exhibits a high initial discharge capacity of 1361 mAh g ⁻¹ at 0.1C and retains 922 mAh g ⁻¹ at 1C. Even at a high sulfur loading of 5.3 mg cm ⁻² , a practical areal capacity of 5.60 mAh cm ⁻² is achieved at 0.1C. Notably, it delivers outstanding cycling stability and maintains its performance over 500 cycles at 4C with a low decay rate of 0.065% per cycle. This study establishes a robust and scalable dual‐atom catalytic platform for achieving durable and high‐performance Li–S batteries.