Fluorinated Hexa‐Peri‐Hexabenzocoronene Derivatives‐Modified CNT Scaffolds Enabling Ultrahigh Capacitance in Hierarchical NiCu‐LDH Hybrid Supercapacitors

Abstract Achieving high capacitance while maintaining rapid charge transport and structural stability remains a major challenge in the design of battery‐type supercapacitor electrodes. Herein, a molecularly engineered strategy is presented for constructing hierarchical hybrid electrodes by integrating petal‐like NiCu‐LDH nanosheets onto 3D HBC‐x (x = H, F, OMe)‐functionalized CNT paper via a one‐step hydrothermal process. The incorporation of HBC effectively mitigates CNT agglomeration and constructs an interconnected conductive framework that enhances charge transport, shortens ion diffusion paths, and reduces internal resistance. Among the variants, fluorinated HBC‐F offers the most pronounced performance improvement, owing to the formation of polar semi‐ionic C–F bonds that elevate local charge density and boost redox kinetics. The resulting NiCu‐LDH@HBC‐F/CNT electrode achieves an ultrahigh specific capacitance of 5270 F g ⁻¹ at 1 A g ⁻¹ , maintaining 80% retention even at 20 A g ⁻¹ . Furthermore, an all‐solid‐state asymmetric device assembled with NiCu‐LDH@HBC‐F/CNT as the positive electrode and CNT paper as the negative electrode delivers an energy density of 21.5 Wh kg ⁻¹ at a power density of 800 W kg ⁻¹ over a wide operating voltage window of 1.6 V. This study presents a novel molecular engineering approach to constructing hierarchical, high‐performance electrode architectures, offering a promising pathway for next‐generation supercapacitor technologies.