Incorporation of Heteroatomic Fe Activates Rapid Catalytic Behaviors of Co₃O₄ Hollow Nanoplates Toward Advanced Lithium–Sulfur Batteries

Abstract Lithium–sulfur (Li–S) battery is a highly attractive energy storage system due to its high capacity and great affordability. However, the parasitic shuttle effect and sluggish redox kinetics are perplexing the fulfillment of efficient battery electrochemistry. To tackle these challenges, herein, a hierarchical and hollow nanoplate assembled by Fe‐doped Co₃O₄ nanosheets (Fe–Co₃O₄ HHNPs) is meticulously designed as an advanced sulfur nanoreactor. The interlaced nanosheets establish a robust and porous network for fast charge transfer and efficient active site exposure. More importantly, the heteroatomic Fe incorporation tailors the electronic structure via local structure distortion and electron redistribution, contributing to massive active sites that lower the energy barrier for sulfur conversions. The resulting sulfur adsorption and catalyzation endow the Li–S cells with minimum capacity decay of 0.08% per cycle over 500 cycles and decent rate performance up to 5 C. Moreover, a high areal capacity of 9.0 mAh cm⁻² after 55 cycles is also achievable under raised sulfur loading of 11 mg cm⁻² and limited electrolyte (E/S = 3.9 µL mg⁻¹). This work provides an elaborate and instructive paradigm for designing catalytic nanoreactors toward superior Li–S electrochemistry.