A Porous Carbon Polyhedron/Carbon Nanotube Based Hybrid Material as Multifunctional Sulfur Host for High‐Performance Lithium‐Sulfur Batteries

Abstract To develop high‐performance lithium‐sulfur (Li−S) batteries, designing and exploring an advanced sulfur cathode with a conductive and polar robust framework is highly significant to suppress the “shuttle effect” of polysulfides and enhance the utilization of active sulfur. Herein, a multifunctional conductive nanohybrid, which acts as a sulfur host, is rationally constructed by inserting/intertwining carbon nanotubes (CNTs) onto Co‐embedded N‐doped porous dual carbon polyhedrons derived from a resorcinol‐formaldehyde (RF) polymer layer enwrapping ZIF‐67 metal‐organic frameworks (MOFs) (Co, N−C@RFC/CNTs). The porous carbon polyhedrons can accommodate a high amount of sulfur owing to their large inner void space; the RF coating carbon layer and the CNTs effectively increase the conductivity and build a network for providing smooth ions/e − pathways; In addition, the polar Co particles and electronegative N heteroatoms synergistically strengthen the chemical adsorption of polysulfides and accelerate the redox reaction of the sulfur cathode. Benefiting from these advantages, the as‐fabricated Co, N−C@RFC/CNTs/S cathode delivers a high reversible capacity of 1373.7 mAh g −1 at 0.1 C, an impressive rate performance with 659.2 mAh g −1 at 2.0 C, and an outstanding cycling stability with an ultralow capacity decay rate of 0.041 % per cycle for 500 cycles at 1.0 C. This work provides a facile and high‐efficiency approach to fabricating excellent‐performance storage materials based on an MOF precursor.