Boosting Spatial Charge Storage in Ion‐Compatible Pores of Carbon Superstructures for Advanced Zinc‐Ion Capacitors

Abstract Capacitive carbon cathodes deliver great potential for zinc‐ion hybrid capacitors (ZHCs) due to their resource abundance and structural versatility. However, the dimension mismatch between the micropores of carbons and hydrated Zn²⁺ ions often results in unsatisfactory charge storage capability. Here well‐arranged heterodiatomic carbon superstructures are reported with compatible pore dimensions for activating Zn²⁺ ions, initiated by the supramolecular self‐assembly of 1,3,5‐triazine‐2,4,6‐triamine and cyanuric acid via in‐plane hydrogen‐bonds and out‐of‐plane π–π interactions. Flower‐shaped carbon superstructures expose more surface‐active motifs, continuous charge‐transport routes, and more importantly, well‐developed pores. The primary subnanopores of 0.82 nm are size‐exclusively accessible for solvated Zn²⁺ ions (0.86 nm) to maximize spatial charge storage, while rich mesopores (1–3 nm) allow for high‐kinetics ion migration with a low activation energy. Such favorable superstructure cathodes contribute to all‐round performance improvement for ZHCs, including high energy density (158 Wh kg⁻¹), fast‐charging ability (50 A g⁻¹), and excellent cyclic lifespan (100 000 cycles). An anion−cation hybrid charge storage mechanism is elucidated for superstructure cathode, which entails alternate physical uptake of Zn²⁺/CF₃SO₃⁻ at electroactive pores and bipedal chemical binding of Zn²⁺ to electronegative carbonyl/pyridine motifs. This work expands the design landscape of carbon superstructures for advanced energy storage.