Modulating the Coordination Chemistry of Cobalt Catalytic Sites by Ruthenium Species to Accelerate the Polysulfide Conversion Kinetics in Lithium‐Sulfur Batteries

The performance of lithium‐sulfur batteries is compromised by the loss of sulfur as dissolved polysulfides in the electrolyte and consequently the polysulfide redox shutting effect. Accelerating the conversion kinetics of polysulfide intermediates into sulfur or lithium sulfide through electrocatalysis has emerged as a root‐cause solution. Co−N−C composite electrocatalyst is commonly used for this purpose. It is illustrated here that how the effectiveness can be improved by modulating the coordination chemistry of Co−N−C catalytic sites through introducing Ru species (RuCo−NC). The well‐dispersed Ru in the Co−NC carbon matrix altered the total charge distribution over the Co−N−C catalytic sites and led to the formation of electron‐rich Co−N, which is highly active for the polysulfide conversion reactions. Using Ru to modulate the electronic structure in the Co−N−C configuration and the additional catalytic sites over the Ru−Nx species can manifest optimal adsorption behavior of polysulfides. Consequently, the sulfur cathode with RuCo−NC can reduce the capacity fade rate from 0.11 % per cycle without catalyst (initial capacity of 701 mAh g−1) to 0.054 % per cycle (initial capacity of 1074 mAh g−1) over 400 cycles at 0.2 C rate. The results of this study provide the evidence for a feasible catalyst modification strategy for the polysulfide electrocatalysis. The well‐dispersed Ru in the Co−NC carbon matrix altered the total charge distribution over the Co−N−C catalytic sites and led to the formation of electron‐rich Co−N, which is highly active for the polysulfide conversion reactions. Additionally, introducing Ru in the Co−NC matrix provided additional catalytic sites over the Ru−Nx species to manifest optimal adsorption behavior of polysulfides.