Abstract

Sponge‐like composites assembled by cobalt sulfides quantum dots (Co 9 S 8 QD), mesoporous hollow carbon polyhedral (HCP) matrix, and a reduced graphene oxide (rGO) wrapping sheets are synthesized by a simultaneous thermal reduction, carbonization, and sulfidation of zeolitic imidazolate frameworks@GO precursors. Specifically, Co 9 S 8 QD with size less than 4 nm are homogenously embedded within HCP matrix, which is encapsulated in macroporous rGO, thereby leading to the double carbon‐confined hierarchical composites with strong coupling effect. Experimental data combined with density functional theory calculations reveal that the presence of coupled rGO not only prevents the aggregation and excessive growth of particles, but also expands the lattice parameters of Co 9 S 8 crystals, enhancing the reactivity for sodium storage. Benefiting from the hierarchical porosity, conductive network, structural integrity, and a synergistic effect of the components, the sponge‐like composites used as binder‐free anodes manifest outstanding sodium‐storage performance in terms of excellent stable capacity (628 mAh g −1 after 500 cycles at 300 mA g −1 ) and exceptional rate capability (529, 448, and 330 mAh g −1 at 1600, 3200, and 6400 mA g −1 ). More importantly, the synthetic method is very versatile and can be easily extended to fabricate other transition‐metal‐sulfides‐based sponge‐like composites with excellent electrochemical performances.