Electrocatalysts are extensively employed to suppress the shuttling effect in lithium-sulfur (Li-S) batteries. However, it remains challenging to probe the sulfur redox reactions and mechanism at the electrocatalyst/LiPS interface after the active sites are covered by the solid discharge products Li₂S/Li₂S₂. Here, we demonstrate the intrinsic autocatalytic activity of the Li₂S (100) plane towards lithium polysulfides on single-atom nickel (SANi) electrocatalysts. Guided by theoretical models and experimental data, it is concluded that LiPS dissociates into Li₂S₂ and short-chain LiPS on the Li₂S (100) plane. Subsequently, Li₂S₂ undergoes further lithiation to Li₂S on the Li₂S (100) surface, generating a new Li₂S (100) layer, thus enabling the autocatalytic formation of a new Li₂S (100) surface. Benefiting from the autocatalytic growth of Li₂S, the concentration of LiPS in the electrolyte remains at a lower level, enabling Li-S batteries under high loading and low electrolyte conditions to exhibit superior electrochemical performance.

Regulating the transformation of sulfur species is the key to improving the electrochemical performance of lithium‐sulfur (Li−S) batteries, in particular, to accelerate the reversible conversion between solid phase Li₂S₂ and Li₂S. Herein, we introduced Spidroin, which is a main protein in spider silk, as a dual functional separator coating in Li−S batteries to effectively adsorb polysulfides via the sequence of amino acids in its primary structure and regulate Li⁺ flux through the β‐sheet of its secondary structure, thus accelerating the reversible transformation between Li₂S₂ and Li₂S. Spidroin‐based Li−S cells exhibited an exceptional electrochemical performance with a high specific capacity of 744.1 mAh g⁻¹ at 5 C and a high areal capacity of 7.5 mAh cm⁻² at a low electrolyte‐to‐sulfur (E/S) ratio of 6 μL mg_s⁻¹ and a sulfur loading of 8.6 mg_s cm⁻².

Commercial graphite anode has advantages such as low potential platform, high electronic conductivity, and abundant reserves. However, its theoretical capacity is only 372 mA h g⁻¹. High-energy lithium-ion batteries have been a research hotspot. The Si anode has an extremely high specific capacity, but its application is hindered by defects such as large volume changes, poor electronic conductivity, and a small lithium-ion diffusion coefficient. Here, the Si/thermally reduced graphite oxide@carbon (Si/RGtO@C) composite was fabricated by electrostatic self-assembly followed by thermal treatment. The RGtO synergistic carbon coating layer can effectively compensate for the low electronic conductivity and buffer the volume expansion effect of the Si nanoparticles during charge/discharge cycles. The Si/RGtO@C anode demonstrated a significantly increased capacity compared to the RGtO. After 300 cycles, Si/RGtO@C kept a discharged capacity of 367.6 mA h g⁻¹ at a high current density of 1.0 A g⁻¹. The Si/RGtO@C anode shows an application potential for commercial high-energy lithium-ion batteries.

Lithium–sulfur (Li-S) batteries offer a high theoretical energy density but suffer from poor cycling stability and polysulfide shuttling, which limits their practical application. To address these challenges, we developed a PANI-modified MoS₂-NG composite, where MoS₂ nanoflowers were uniformly grown on graphene oxide (GO) through PANI modification, resulting in an increased interlayer spacing of MoS₂. This expanded spacing exposed more active sites, enhancing polysulfide adsorption and catalytic conversion. The composite was used to prepare MoS₂-NG/PP separators for Li-S batteries, which achieved a high specific capacity of 714 mAh g⁻¹ at a 3 C rate and maintained a low capacity decay rate of 0.085% per cycle after 500 cycles at 0.5 C. The larger MoS₂ interlayer spacing was key to improving redox reaction kinetics and suppressing the shuttle effect, making the MoS₂-NG composite a promising material for enhancing the performance and stability of Li-S batteries.