Oxidation States Regulation of Cobalt Active Sites through Crystal Surface Engineering for Enhanced Polysulfide Conversion in Lithium–Sulfur Batteries

In this work, unique Co₃ O₄ /N-doped reduced graphene oxide (Co₃ O₄ /N-rGO) composites as favorable sulfur immobilizers and promoters for lithium-sulfur (Li-S) batteries are developed. The prepared Co₃ O₄ nanopolyhedrons (Co₃ O₄ -NP) and Co₃ O₄ nanocubes mainly expose (112) and (001) surfaces, respectively, with different atomic configurations of Co²⁺ /Co³⁺ sites. Experiments and theoretical calculations confirm that the octahedral coordination Co³⁺ (Co³⁺ _Oh ) sites with different oxidation states from tetrahedral coordination Co²⁺ sites optimize the adsorption and catalytic conversion of lithium polysulfides. Specially, the Co₃ O₄ -NP crystals loaded on N-rGO expose (112) planes with ample Co³⁺ _Oh active sites, exhibiting stronger adsorbability and superior catalytic activity for polysulfides, thus inhibiting the shuttle effect. Therefore, the S@Co₃ O₄ -NP/N-rGO cathodes deliver excellent electrochemical properties, for example, stable cyclability at 1 C with a low capacity decay rate of 0.058% over 500 cycles, superb rate capability up to 3 C, and high areal capacity of 4.1 mAh cm^-2 . This catalyst's design incorporating crystal surface engineering and oxidation state regulation strategies also provides new approaches for addressing the complicated issues of Li-S batteries.