A Transmetalation Synthetic Strategy to Engineer Atomically Dispersed MnN₂O₂ Electrocatalytic Centers Driving High-Performance LiS Battery

Sluggish sulfur redox reaction (SROR) kinetics accompanying lithium polysulfides (LiPSs) shuttle effect becomes a stumbling block for commercial application of LiS battery. High-efficient single atom catalysts (SACs) are desired to improve the SROR conversion capability; however, the sparse active sites as well as partial sites encapsulated in bulk-phase are fatal to the catalytic performance. Herein, high loading (5.02 wt.%) atomically dispersed manganese sites (MnSA) on hollow nitrogen-doped carbonaceous support (HNC) are realized for the MnSA@HNC SAC by a facile transmetalation synthetic strategy. The thin-walled hollow structure (≈12 nm) anchoring the unique trans-MnN₂O₂ sites of MnSA@HNC provides a shuttle buffer zone and catalytic conversion site for LiPSs. Both electrochemical measurement and theoretical calculation indicate that the MnSA@HNC with abundant trans-MnN₂O₂ sites have extremely high bidirectional SROR catalytic activity. The assembled LiS battery based on the MnSA@HNC modified separator can deliver a large specific capacity of 1422 mAh g⁻¹ at 0.1 C and stable cycling over 1400 cycles with an ultralow decay rate of 0.033% per cycle at 1 C. More impressively, a flexible pouch cell on account of the MnSA@HNC modified separator may release a high initial specific capacity of 1192 mAh g⁻¹ at 0.1 C and uninterruptedly work after the bending-unbending processes.