To overcome the shuttle effect in Li–S batteries, novel biomimetic molecule catalysts are synthesized by grafting hemin molecules to three functionalized carbon nanotube systems (CNTs–COOH, CNTs–OH, and CNTs–NH2). The Li–S battery using the CNTs–COOH@hemin cathode exhibits the optimal initial specific capacity (1637.8 mAh g−1) and cycle durability (up to 1800 cycles). Various in situ characterization techniques, such as Raman spectroscopy, Fourier‐transform infrared reflection absorption spectroscopy, and UV–vis spectroscopy, combined with density functional theory computations are used to investigate the structure–reactivity correlation and the working mechanism in the Li–S system. It is demonstrated that the unique structure of the CNTs‐COOH@hemin composite with good conductivity and adequate active sites resulting from molecule catalyst as well as the strong absorption to polysulfides entrapped by the coordinated Fe(III) complex with FeO bond enables the homogeneous dispersion of S, facilitates the catalysis and conversion of polysulfides, and improves the battery's performance.

The sluggish reaction kinetics at the cathode/electrolyte interface of lithium–sulfur (Li–S) batteries limits their commercialization. Herein, we show that a dual-regulation system of iron phthalocyanine (FePc) and octafluoronaphthalene (OFN) decorated on graphene (Gh), denoted as Gh/FePc+OFN, accelerates the interfacial reaction kinetics of lithium polysulfides (LiPSs). Multiple in situ spectroscopy techniques and ex situ X-ray photoelectron spectroscopy combined with density functional theory calculations demonstrate that FePc acts as an efficient anchor and scissor for the LiPSs through Fe···S coordination, mainly facilitating their liquid–liquid transformation, whereas OFN enables Li-bond interaction with the LiPSs, accelerating the kinetics of the liquid–solid nucleation and growth of Li2S. This dual-regulation system promotes the smooth conversion reaction of sulfur, thereby improving the battery performance. A Gh/FePc+OFN-based Li–S cathode delivered an ultrahigh initial capacity of 1604 mAh g–1 at 0.2 C, with an ultralow capacity decay rate of 0.055% per cycle at 1 C over 1000 cycles.

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%.

The complicated reactions at the cathode–electrolyte interface in Li–S batteries are a large barrier for their successful commercialization. Herein, we developed a molecular design strategy and employed three small molecules acting as interfacial mediators to the cathodes of Li–S batteries. The theoretical calculation results show that the incorporation of tris­(4-fluorophenyl)­phosphine (TFPP) has a strong binding performance. The experimental results demonstrate that the strong chemical interactions between polysulfides and the F, P atoms in TFPP not only modify the kinetics of the electrochemical processes in the electrolyte but also promote the formation of short-chain clusters (Li2S x , x = 1, 2, 3, and 4) at the interface during the charge–discharge process. As a result, an optimized electrode exhibits a low capacity decay rate of 0.042% per cycle when the current rate is increased to 5 C over 1000 cycles.

A high-performance catalyst, O-doped Sb2S3 nanosheets (SS-O NSs), is synthesized and introduced into lithium–sulfur batteries. Owing to their good conductivity, strong adsorbability/catalytic effect to polysulfides and fast Li+ diffusion, the...