Enhanced Chemisorption and Catalytic Effects toward Polysulfides by Modulating Hollow Nanoarchitectures for Long‐Life Lithium–Sulfur Batteries

Hollow nanostructures with intricate interior and catalytic effects hold great promise for the construction of advanced lithium-sulfur batteries. Herein, a double-shelled hollow polyhedron with inlaid cobalt nanoparticles encapsulated by nitrogen-doped carbon (Co/NC) nanodots (Co-NC@Co9 S8 /NPC) is reported, which is acquired by using imidazolium-based ionic-polymer-encapsulated zeolitic imidazolate framework-67 as a core-shelled precursor. The Co/NC nanodots promote redox kinetics and chemical adsorbability toward polysulfides, while the interconnected double shells serve as a nanoscale electrochemical reaction chamber, which effectively suppresses the polysulfide shuttling and accelerates ion/electron transport. Benefiting from structural engineering and reaction kinetics modulation, the Co-NC@Co9 S8 /NPC-S electrode exhibits high cycling stability with a low capacity decay of 0.011% per cycle within 2000 cycles at 2 C. The electrode still shows high rate performance and cyclability over 500 cycles even in the case of high sulfur loading of 4.5 mg cm-2 and 75 wt% sulfur content. This work provides one type of new hollow nanoarchitecture for the development of advanced Li-S batteries and other energy storage systems.