We develop a novel microtemplate strategy to prepare unique carbon aerogels. The designed cathode materials present excellent electrochemical performance.

A novel net channel and N‐doping carbon aerogel (CA) are successfully prepared by an in situ and facile method via polyimide (PI) inducting for lithium–sulfur (Li–S) batteries. The PI‐directing carbon aerogel (PI‐CA) presents a cross‐linked framework, abundant porosity, and a high specific surface area. PI‐CA spheres present effective immobilizing polysulfides and high loading sulfur for a Brunauer–Emmett–Teller (BET) surface area of 2039.4 m2 g−1 and N‐doping via physical and chemical adsorption. The Li–S batteries with PI‐CA as cathode matrix exhibit excellent performance. In particular, the initial specific capacity of 2PI‐CA/S with sulfur content of 73.8 wt% delivers 1338 mAh g−1 and remains at 1102 mAh g−1 after 100 cycles at 0.2 C. The enhanced electrochemical performance mainly benefits from the mesh structure of the composite and the interaction between nitrogen and lithium polysulfide. The theoretical calculation by density functional theory (DFT) further supports the template effect of PI and the anchoring mechanism of polysulfides.

A cage‐type composite was successfully prepared by attaching p‐sulfonatocalix[4]arene to a porous activated carbon aerogel (ACA). The resulting composite showed a high specific surface area of 1620.7 m2 g−1 and a high sulfur loading of 2.5 mg cm−2. The calixarene is uniformly dispersed on the carbon spheres and efficiently captures polysulfides by interaction with the sulfonate groups. Meanwhile, the cross‐linked porous structure of the composite restricts the migration of polysulfides. The cathode delivers an outstanding electrochemical performance with an initial capacity of 1304.7 mAh g−1 at 0.2 C. Furthermore, it displays excellent long‐term cycling stability, maintaining 884.7 mAh g−1 after 300 cycles at 0.5 C. Density functional theory (DFT) adsorption calculations support the strong interaction between the calixarenes and polysulfides and reveal the capture mechanism.

Scheme 1. Schematic illustration of synthetic, assembly, and related processes of PEG-Ag-CA/S.