From Mononuclear to Trinuclear: Tailoring Coordination Metal Cluster Node for High‐Energy Li‐S Batteries

ABSTRACT As a new‐generation high‐energy‐density energy storage system, the commercialization of lithium‐sulfur (Li‐S) batteries remains hindered by the polysulfide shuttle effect and sluggish redox kinetics. This study investigated the catalytic performance of mononuclear cobalt (MCo) and trinuclear cobalt (TCo) catalysts in Li‐S batteries. By precisely regulating the nuclear number and spatial configuration of metal nodes, we revealed the enhancing effect of the multinuclear cooperative catalytic mechanism on the kinetics of sulfur redox. TCo provides multiple catalytic sites and forms a continuous electron‐conducting network through intermetallic electron coupling, significantly accelerating the sulfur redox kinetics. Molecular orbital theory and density functional theory calculations indicate that the high‐spin Co 3+ in TCo exhibits enhanced adsorption capacity toward polysulfides, effectively mitigating the shuttle effect. Benefiting from this synergistic effect, the battery with TCo separator achieves a specific capacity of 1296.7 mAh g −1 at 0.1 C and exhibits a degradation rate of only 0.088% per cycle after 500 cycles at 1 C. This study provides a new horizon for developing next‐generation Li‐S battery catalysts.