Cation-driven self-assembly of core–shell covalent organic frameworks@Ti3CN MXene nanospheres for high-performance aqueous zinc-ion hybrid supercapacitors

Rechargeable aqueous Zn-ion hybrid supercapacitors (ZISCs) with the superiorities of high theoretical capacity, low redox potential and aqueous electrolytes with superior ionic conductivity (∼1 S cm−1) are promising energy storage systems. However, a primary concern persists due to the absence of cathode materials with both high energy densities and satisfactory cycling stability for robust ZISCs. In this study, we design a spherical core–shell covalent organic frameworks@Ti3CN MXene (CM-P) cathode via a cation-driven electrostatic self-assembly strategy. The CM-P with the constructed heterostructures shows both well-organized pore channels and excellent intrinsic conductivity, facilitating fast accessibility to intrinsic redox-active sites (such as C = O and N), and promoting effective ion diffusion characterized by low energy barriers. Consequently, the CM-P cathodes demonstrate excellent electrochemical performance, featuring an ultrahigh specific capacity of 260 mAh/g at 0.1 A, a high-rate capability with 68 % retention at 1 A/g, and long-term cycling stability. First-principle calculations elucidate that the enhanced charge-storage mechanism relies on the heterostructures of CM-P, accelerating ion adsorption/diffusion and electron transfer. Furthermore, the assembled CM-P//Zn ZISCs devices show a high energy density of 217.1 Wh kg−1 along with power density of 22.3 kW kg−1. This work provides an innovative approach to design COFs-based heterostructures for advanced ZISCs.