Nanofiber‐Interlocked V2CTx Hosts Enriched with 3D Lithiophilic and Sulfophilic Sites for Long‐Life and High‐Rate Lithium–Sulfur Batteries

Abstract Lithium–sulfur batteries (LSBs) currently face challenges including lithium polysulfide shuttling, sluggish sulfur redox kinetics, severe lithium dendrite growth, and volume change. Herein, an advanced dual‐functional host is designed by embedding 3D N‐doped carbon fibers with abundant 2D V 2 CT x nanosheets (N/CF@V 2 CT x ). The N‐doped carbon fibers act as “thread” to connect the V 2 CT x nanosheets and form a unique open 3D macroporous structure. This structure effectively prevents the restacking of the V 2 CT x nanosheets and exposes their lithiophilic and sulfurophilic sites. Consequently, the N/CF@V 2 CT x host effectively suppresses the shuttling of LiPSs and improves the cathodic kinetics. Furthermore, the 3D‐ordered porous skeleton integrated with abundant lithophilic sites enables uniform Li deposition and homogeneous Li‐ion flux, thereby inhibiting dendrite growth and mitigating volume expansion. The as‐assembled LSBs exhibit excellent rate capability (640 mAh g −1 at 15 C) and outstanding cycling stability (0.019% capacity decay per cycle throughout 1200 cycles at 1 C). Moreover, the pouch cell assembled with the N/CF@V 2 CT x host demonstrates a high energy density of 350 Wh kg −1 and good cycling stability. This research presents a promising approach to address the challenges of both the sulfur cathode and the lithium anode comprehensively and effectively in working LSBs.