Low-Coordinated Zn–N2 Sites as Bidirectional Atomic Catalysis for Room-Temperature Na–S Batteries

The rational design of advanced catalysts for sodium-sulfur (Na-S) batteries is important but remains challenging due to the limited understanding of sulfur catalytic mechanisms. Here, we propose an efficient sulfur host consisting of atomic low-coordinated Zn-N₂ sites dispersed on N-rich microporous graphene (Zn-N₂@NG), which realizes state-of-the-art sodium-storage performance with a high sulfur content of 66 wt %, high-rate capability (467 mA h g^-1 at 5 A g^-1), and long cycling stability for 6500 cycles with an ultralow capacity decay rate of 0.0062% per cycle. Ex situ methods combined with theoretical calculations demonstrate the superior bidirectional catalysis of Zn-N₂ sites on sulfur conversion (S₈ ↔ Na₂S). Furthermore, in situ transmission electron microscopy was applied to visualize the microscopic S redox evolution under the catalysis of Zn-N₂ sites without liquid electrolytes. During the sodiation process, both surface S nanoparticles and S molecules in the mircopores of Zn-N₂@NG quickly convert into Na₂S nanograins. During the following desodiation process, only a small part of the above Na₂S can be oxidized into Na₂S_x. These results reveal that, without liquid electrolytes, Na₂S is difficult to be decomposed even with the assistance of Zn-N₂ sites. This conclusion emphasizes the critical role of liquid electrolytes in the catalytic oxidation of Na₂S, which was usually ignored by previous works.