Tuning the Local Coordination of CoP1–xSx between NiAs- and MnP-Type Structures to Catalyze Lithium–Sulfur Batteries

The slow conversion and rapid shuttling of polysulfides remain major challenges that hinder the practical application of lithium-sulfur (Li-S) batteries. Efficient catalysts are needed to accelerate the conversion and suppress the shuttling. However, the lack of a rational understanding of catalysis poses obstacles to the design of catalysts, thereby limiting the rapid development of Li-S batteries. Herein, we theoretically analyze the modulation of the electronic structure of CoP_1-xS_x caused by the NiAs-to-MnP-type transition and its influence on catalytic activity. We found that the interacting d-orbitals of the active metal sites play a determining role in adsorption and catalysis, and the optimal d_z²-, d_xz-, and d_yz-orbitals in an appropriately distorted five-coordinate pyramid enable higher catalytic activity compared with their parent structures. Finally, rationally designed catalysts and S were electrospun into carbonized nanofibers to form nanoreactor chains for use as cathodes. The resultant Li-S batteries exhibited superior properties over 1000 cycles with only a decay rate of 0.031% per cycle and demonstrated a high capacity of 887.4 mAh g^-1 at a high S loading of 10 mg cm^-2. The structural modulation and bonding analyses in this study provide a powerful approach for the rational design of Li-S catalysts.