Molybdenum Carbide Electrocatalyst In Situ Embedded in Porous Nitrogen‐Rich Carbon Nanotubes Promotes Rapid Kinetics in Sodium‐Metal–Sulfur Batteries

Abstract This is the first report of molybdenum carbide‐based electrocatalyst for sulfur‐based sodium‐metal batteries. MoC/Mo₂C is in situ grown on nitrogen‐doped carbon nanotubes in parallel with formation of extensive nanoporosity. Sulfur impregnation (50 wt% S) results in unique triphasic architecture termed molybdenum carbide–porous carbon nanotubes host (MoC/Mo₂C@PCNT–S). Quasi‐solid‐state phase transformation to Na₂S is promoted in carbonate electrolyte, with in situ time‐resolved Raman, X‐ray photoelectron spectroscopy, and optical analyses demonstrating minimal soluble polysulfides. MoC/Mo₂C@PCNT–S cathodes deliver among the most promising rate performance characteristics in the literature, achieving 987 mAh g⁻¹ at 1 A g⁻¹, 818 mAh g⁻¹ at 3 A g⁻¹, and 621 mAh g⁻¹ at 5 A g⁻¹. The cells deliver superior cycling stability, retaining 650 mAh g⁻¹ after 1000 cycles at 1.5 A g⁻¹, corresponding to 0.028% capacity decay per cycle. High mass loading cathodes (64 wt% S, 12.7 mg cm⁻²) also show cycling stability. Density functional theory demonstrates that formation energy of Na₂S_x (1 ≤ x ≤ 4) on surface of MoC/Mo₂C is significantly lowered compared to analogous redox in liquid. Strong binding of Na₂S_x (1 ≤ x ≤ 4) on MoC/Mo₂C surfaces results from charge transfer between the sulfur and Mo sites on carbides’ surface.