Abstract: Structured design helps to play out the coordination advantage and optimize the performance of electrochemical reactions. In this work, hierarchical hollow microspheres (Co₃S₄@NiCo₂S₄) with unique core-shell heterostructure were successfully prepared through simple template and solvothermal methods. Thanks to the hollow structure, cross-linked nanowire arrays, and in-situ coating of zeolite imidazole framework (ZIF), Co₃S₄@NiCo₂S₄ demonstrated excellent electrochemical performance with a specific capacitance of up to 2697.7 F g^-1 at 1 A g^-1 and cycling stability of 80.5% after 5000 cycles. The covalent organic framework (COF) derived nano carbon, which had undergone secondary calcination and ZnCl₂ activation, also exhibited excellent double-layer energy storage performance. Compared to a single calcination, the incredible increase in capacitance was up to 208.5 times greater, reaching 291.9 F g^-1 at 1 A g^-1 while maintaining ultra-high rate performance (81.0% at 20 A g^-1). The hybrid supercapacitor, assembled with Co₃S₄@NiCo₂S₄ as the cathode and COF-derived carbon as the anode, exhibited an extremely high energy density (79.7 Wh kg^-1 at 693.5 W kg^-1) and excellent cyclic stability (maintained 79.3% after 10,000 cycles of 20 A g^-1), further explaining the reliable and practical characteristics. This work provided reference for the structural optimization of transition metal sulfides and the high-temperature activation of COF-derived carbon.

Key words: Core-shell heterostructures, Metal organic frameworks, Covalent organic framework derived carbon, Hybrid supercapacitors