LAUSR

The development of highly sophisticated biomimetic models is significant yet remains challenging in the electrochemical energy storage field. Lithium–sulfur (Li–S) cells with high sulfur content and high‐sulfur‐loading cathodes are urgently required to meet the fast‐growing demand for electronic devices. Nevertheless, such cathode materials generally suffer from large sulfur agglomeration, nonporous structure, and insufficient conductivity, leading to rapid capacity decay and low sulfur utilization. Herein, inspired by rough endoplasmic reticulum, a 2D polystyrene (PS)‐brush‐based (G‐g‐PS) superhigh‐sulfur‐content (96 wt%) composite(G‐g‐sPS@S) is fabricated via the vulcanization reaction. The vulcanized PS side‐chains and their S8 composites on the nanosheet surface can efficiently provide sulfur species, and the intersheet interstitial pores can provide rapid mass‐transfer channels for redox reactions of sulfur species. Furthermore, the highly sulfophilic vulcanized PS side‐chains are able to effectively inhibit the shuttle effect of polysulfides and regulate their redox process. With these merits, the cells with G‐g‐sPS@S cathodes exhibit an ultralow decay rate of 0.02% per cycle over 400 cycles at 2 C and deliver a superior areal capacity of 12.6 mAh cm−2 even with a high sulfur loading of 10.5 mg cm−2.