Cofactor-Assisted Artificial Enzyme with Multiple Li-Bond Networks for Sustainable Polysulfide Conversion in...

Lithium-sulfur batteries possess high theoretical energy density but suffer from rapid capacity fade due to the shuttling and sluggish conversion of polysulfides. Aiming at these problems, a biomimetic design of cofactor-assisted artificial enzyme catalyst, melamine (MM) crosslinked hemin on carboxylated carbon nanotubes (CNTs) (i.e., [CNTs-MM-hemin]), is presented to efficiently convert polysulfides. The MM cofactors bind with the hemin artificial enzymes and CNT conductive substrates through FeN₅ coordination and/or covalent amide bonds to provide high and durable catalytic activity for polysulfide conversions, while π-π conjugations between hemin and CNTs and multiple Li-bond networks offered by MM endow the cathode with good electronic/Li⁺ transmission ability. This synergistic mechanism enables rapid sulfur reaction kinetics, alleviated polysulfide shuttling, and an ultralow (<1.3%) loss of hemin active sites in electrolyte, which is ≈60 times lower than those of noncovalent crosslinked samples. As a result, the Li-S battery using [CNTs-MM-hemin] cathode retains a capacity of 571 mAh g^-1 after 900 cycles at 1C with an ultralow capacity decay rate of 0.046% per cycle. Even under raising sulfur loadings up to 7.5 mg cm^-2 , the cathode still can steadily run 110 cycles with a capacity retention of 83%.