A <scp>3D</scp> Heterostructural Composite Comprising <scp>MOF</scp>‐Derived Ni(<scp>OH</scp>)₂ and <scp>NiAl LDH</scp> on <scp>rGO</scp> for Supercapacitors

Comprehensive Summary The development of high‐performance cathode materials through rational heterointerface engineering remains pivotal for advancing hybrid supercapacitors (HSCs) technologies. Here, we construct a three‐dimensional ternary heterostructure composite Ni(OH) 2 /NiAl LDH/rGO (N‐OH/NA/rG) by sequential integration of metal‐organic frameworks (MOF)‐derived Ni(OH) 2 , NiAl LDH and reduced graphene oxide (rGO). The covalent anchoring of NiAl LDH nanosheets on oxygen‐functionalized rGO substrates mitigates restacking issues, establishing a conductive network with enhanced charge transfer kinetics. The alkaline etching of Ni‐MOF precursors preserves their hierarchical porosity while converting to pseudocapacitive Ni(OH)₂. Synergistic effects among components yield increased active site density, dual charge storage mechanisms, and optimized ion diffusion pathways. The optimized composite achieves a high specific capacitance of 1481.7 F/g at 1A/g, along with excellent rate capability and cycle performance, establishing a new paradigm for designing multi‐component heterostructure electrodes through MOF‐derived interface engineering. Furthermore, the N‐OH/NA/rG//AC HSC device demonstrates a high power density and energy density, coupled with long‐term cycle stability, underscoring the substantial potential of N‐OH/NA/rG as a cathode material for HSCs.