LAUSR

The development of a suitable cathode host that withstands high sulfur content/loading and low electrolyte/sulfur (E/S) ratio is particularly important for practically sustainable Li–S batteries. Herein, a facile approach is utilized to prepare free‐standing 3D cathode substrates comprising nitrogen‐doped carbon (N‐C) scaffold and metal–organic framework derived interconnected chain‐like hollow N‐C nanocages, forming a highly porous N‐C nanofiber (HP‐N‐CNF) framework. The N‐C skeleton provides highly conductive pathways for fast lithium ion/electron diffusion. The hollow interconnected N‐C nanocages not only offer enough space to absorb a high volume of active material but also effectively channelize severe volume stress during the electrochemical performance. The Li–S cell utilizing HP‐N‐CNF as cathode host displays exceptional battery parameters with high effective sulfur content (83.2 wt%), ultrahigh sulfur loading (14.3 mg cm–2), and low E/S ratio (6.8 μL mg–1). The Li–S cell exhibits a maximum areal capacity of 12.2 mAh cm–2 which stabilizes at ≈5.5 mAh cm–2 after the 130th cycle at 0.05 C‐rate and is well above the theoretical threshold. Therefore, the proposed unique nanostructure synthesis approach would open new frontiers for developing more realistic and sustainable host materials with feasible battery parameters for various energy storage applications.