Ultralong-Life Zinc-Ion Hybrid Capacitors Enabled by Hydrogen-Bonding-Guided Nanosheet-Assembled Carbon Superstructures

Carbon superstructures with tailored morphology and multiscale hierarchy are beneficial in attaining excellent capacitive performance and sustained electrochemical performance during long-term cycling in Zn-ion hybrid capacitors, but their customized design is still unclear. Herein, we design a hydrogen-bond-guided nanosheet assembly approach to construct morphologically distinct origami fan-shaped carbon superstructures (FCS-8) for zinc-ion storage with concurrently high capacitive properties and durability. The process begins with the formation of nanosheets, driven by interaction between the –NH2 groups of m-phenylenediamine (donor) and the carbonyl or carboxyl groups of pyromellitic dianhydride (acceptor). These nanosheets then stack and densify directionally, guided by sustained hydrogen bonding to form a superstructure. The well-ornate FCS-8, assembled from nanosheets that create interconnected open nanoporous channels, possesses multiscale hierarchy along with a remarkably large surface area (3143 m2 g–1), providing continuous charge transport pathways for rapid Zn-ion diffusion with a minimal energy barrier (3.3 kJ mol–1), ensuring abundant zincophilic sites and collectively contributing to the superior zinc-ion storage metrics. Notably, FCS-8 demonstrates a substantial capacity of 264.7 mAh g–1, along with a high energy density of 168.9 Wh kg–1 and remarkable long-term durability with stability over 300,000 cycles at a current density of 20 A g–1. The outstanding electrochemical performance is chiefly governed by a highly efficient charge storage mechanism, which involves the alternating adsorption of the Zn2+ ion and CF3SO3– ions, together with a chemical redox reaction between Zn2+ ions and pyridine and carbonyl functional groups at the numerous, well-exposed zincophilic sites embedded into robust, well-ornate superstructures featuring multiscale hierarchies. This work unlocks a new dimension for designing superstructural carbons toward advanced energy storage.