Hierarchically porous carbons (PCs) derived from hypercrosslinked polymers (HCPs) have emerged as promising anode materials owing to their tunable pore architecture and abundant defect sites. However, precise regulation of the microcrystalline structure and pore configuration remains a critical challenge for achieving fast potassium-ion transport. Herein, an aromatic ring axial extension of HCPs monomer regulation strategy is proposed to construct the HCPs structure by employing aromatic monomers with progressively extended conjugated planes, including benzene, naphthalene, and anthracene. After pyrolysis, a series of PCs with systematically evolved microcrystalline and pore structures are obtained. The results revealed that increasing the planar aromatic ring number promotes the formation of ordered graphitic domains and induces a transformation of pore architecture from open pores to closed pore frameworks. In particular, anthracene-based HCPs derived porous carbon (PC) exhibits an interwoven long-range ordered microcrystalline structure and the highest closed pore volume (0.062 cm3 g−1), which is attributed to the enhanced graphitization of PCs effect of extended polycyclic aromatic hydrocarbon units. As a result, A-PC exhibit superior reversible capacity (214 mAh g−1 after 200 cycles) at a current density of 0.05 A g−1 and outstanding rate performance (0.05-5 A g−1). Kinetic analysis and in-situ XRD measurements reveal a sequential potassium-ion storage mechanism. Furthermore, a potassium-ion hybrid capacitor (PIHC) constructed with optimized A-PC anode delivers a high energy density of 126 Wh kg−1 at power density of 338 W kg−1 and maintains stable for over 4000 cycles at 1 A g−1. This research offers new insights into the molecular design strategies for regulating carbon microcrystalline evolution and pore structure as well as promotes the advancement of high rate potassium-ion storage in PC materials.


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