A Universal Spinning‐Coordinating Strategy to Construct Continuous Metal–Nitrogen–Carbon Heterointerface with Boosted Lithium Polysulfides Immobilization for 3D‐Printed Li—S Batteries

Constructing intimate coupling between transition metal and carbon nanomaterials is an effective means to achieve strong immobilization of lithium polysulfides (LiPSs) in the applications of lithium–sulfur (Li—S) batteries. Herein, a universal spinning‐coordinating strategy of constructing continuous metal–nitrogen–carbon (M—N—C, M = Co, Fe, Ni) heterointerface is reported to covalently bond metal nanoparticles with nitrogen‐doped porous carbon fibers (denoted as M/M—N@NPCF). Guided by theoretical simulations, the Co/Co—N@NPCF hybrid is synthesized as a proof of concept and used as an efficient sulfur host material. The polarized Co—N—C bridging bonds can induce rapid electron transfer from Co nanoparticles to the NPCF skeleton, promoting the chemical anchoring of LiPSs to improve sulfur utilization. Hence, the as‐assembled Li—S battery presents a remarkable capacity of 781 mAh g(−1) at 2.0 C and a prominent cycling lifespan with a low decay rate of only 0.032% per cycle. Additionally, a well‐designed Co/Co—N@NPCF‐S electrode with a high sulfur loading of 7.1 mg cm(−2) is further achieved by 3D printing technique, which demonstrates an excellent areal capacity of 6.4 mAh cm(−2) at 0.2 C under a lean‐electrolyte condition. The acquired insights into strongly coupled continuous heterointerface in this work pave the way for rational designs of host materials in Li—S systems.