Asymmetric N-coordinated iron single-atom catalysts supported on graphitic carbon for polysulfide conversion in lithium-sulfur batteries

• The Fe SACs with the asymmetric Fe-N 5 moiety anchored on GCNC were fabricated. • The Fe-N 5 /GCNC is capable of adsorbing LiSPs and accelerating their redox kinetics. • The Li-S cell with the Fe-N 5 /GCNC@PP separator exhibits superior cycling stability. • The assembled device shows an areal capacity as high as 4.49 mAh cm -2 at 0.2C. Lithium-sulfur (Li-S) batteries with extremely high theoretical energy density are expected to be the next-generation energy storage systems. However, the electrochemical performance of Li-S batteries is still restricted by the shuttle effect of lithium polysulfides (LiPSs) resulting from their sluggish conversion kinetics. Herein, we demonstrated a coordination-confinement-pyrolysis strategy to fabricate iron single-atom catalysts (Fe SACs) supported on graphitic carbon nanocapsules (GCNC) by using imine (-RC=N-)-enriched polymer as precursors, aiming at suppressing the shuttle effect in Li-S batteries via simultaneously enhancing LiPSs confinement and catalytic conversion. The in-depth experiment investigations have revealed that the as-obtained N-doped carbon nanocapsules with ample hollow channels and large specific surface area (SSA) enable efficient adsorption and confinement for LiPS intermediates. Further, the isolated Fe SACs anchored on highly conductive graphitic carbon frameworks show an asymmetric N-coordinated active moiety (Fe-N 5 ) that ensures fast redox kinetics of LiPSs and solid Li 2 S/Li 2 S 2 products. As a result, the Li-S cell with a functional separator modified by the Fe-N 5 /GCNC exhibits a much-increased specific capacity of 1125 mAh g −1 at 0.1 C, excellent rate capability of 627 mAh g −1 at 2 C, and remarkable long-term cycling stability with a low capacity decay of 0.0386% per cycle upon 1000 cycles. This work presents a useful strategy to fabricate high-activity SACs coupled with hollow graphitic carbon frameworks and to accelerate the catalytic conversion kinetics of LiPS intermediates for high-performance Li-S batteries.