A Highly Dispersed Cobalt Electrocatalyst with Electron‐Deficient Centers Induced by Boron toward Enhanced Adsorption and Electrocatalysis for Room‐Temperature Sodium–Sulfur Batteries

Abstract As vitally prospective candidates for next‐generation energy storage systems, room‐temperature sodium–sulfur (RT‐Na/S) batteries continue to face obstacles in practical implementation due to the severe shuttle effect of sodium polysulfides and sluggish S conversion kinetics. Herein, the study proposes a novel approach involving the design of a B, N co‐doped carbon nanotube loaded with highly dispersed and electron‐deficient cobalt (Co@BNC) as a highly conductive host for S, aiming to enhance adsorption and catalyze redox reactions. Crucially, the pivotal roles of the carbon substrate in prompting the electrocatalytic activity of Co are elucidated. The experiments and density functional theory (DFT) calculations both demonstrate that after B doping, stronger chemical adsorption toward polysulfides (NaPSs), lower polarization, faster S conversion kinetics, and more complete S transformation are achieved. Therefore, the as‐assembled RT‐Na/S batteries with S/Co@BNC deliver a high reversible capacity of 626 mAh g −1 over 100 cycles at 0.1 C and excellent durability (416 mAh g −1 over 600 cycles at 0.5 C). Even at 2 C, the capacity retention remains at 61.8%, exhibiting an outstanding rate performance. This work offers a systematic way to develop a novel Co electrocatalyst for RT‐Na/S batteries, which can also be effectively applied to other transition metallic electrocatalysts.