LAUSR

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 Na2Sx (1 ≤ x ≤ 4) on surface of MoC/Mo2C is significantly lowered compared to analogous redox in liquid. Strong binding of Na2Sx (1 ≤ x ≤ 4) on MoC/Mo2C surfaces results from charge transfer between the sulfur and Mo sites on carbides’ surface.