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

In this work, unique Co 3 O 4 /N‐doped reduced graphene oxide (Co 3 O 4 /N‐rGO) composites as favorable sulfur immobilizers and promoters for lithium–sulfur (Li–S) batteries are developed. The prepared Co 3 O 4  nanopolyhedrons (Co 3 O 4 ‐NP) and Co 3 O 4  nanocubes mainly expose (112) and (001) surfaces, respectively, with different atomic configurations of Co 2+ /Co 3+ sites. Experiments and theoretical calculations confirm that the octahedral coordination Co 3+ (Co 3+ Oh ) sites with different oxidation states from tetrahedral coordination Co 2+ sites optimize the adsorption and catalytic conversion of lithium polysulfides. Specially, the Co 3 O 4 ‐NP crystals loaded on N‐rGO expose (112) planes with ample Co 3+ Oh active sites, exhibiting stronger adsorbability and superior catalytic activity for polysulfides, thus inhibiting the shuttle effect. Therefore, the S@Co 3 O 4 ‐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.