Arylamine‐Linked Porous Organic Polymers with Abundant Redox‐Active Sites as High‐Capacity and High‐Rate Organic Cathodes for Lithium‐Ion Batteries

Abstract Redox‐active porous organic polymers (POPs) have emerged as promising and sustainable organic cathode materials (OCMs) for lithium‐ion batteries (LIBs). However, their performance is significantly limited by insufficient redox‐active sites and low intrinsic conductivity. Herein, a series of novel arylamine‐linked and bipolar POPs (denoted as HATN‐AQ, HATN‐BQ, HATN‐CBD, and HATN‐PTO) are designed and prepared as OCMs for LIBs. Benefiting from their high density of redox‐active sites, bipolar feature, and arylamine linkage, these POPs exhibited high capacity, high rate, and excellent long‐term cycling stability. Among them, HATN‐PTO displayed an ultrahigh reversible capacity of 329.6 mAh g⁻¹ at 0.2 A g⁻¹ with a high energy density of 716.7 Wh kg⁻¹, outstanding rate performance (208.7 mAh g⁻¹ at 20 A g⁻¹), and superior cycling stability (188.9 mAh g⁻¹ capacity retained after 500 cycles at 1 A g⁻¹). Furthermore, the HATN‐PTO//graphite full battery exhibited a high specific capacity of 227.3 mAh g⁻¹ at 0.2 A g⁻¹ and maintained a high capacity of 99.1 mAh g⁻¹ after 200 cycles at 0.5 A g⁻¹. Ex situ FT‐IR and XPS spectra combined with theoretical calculations are employed to elucidate the dual‐ion storage mechanism. This work provides an effective strategy for designing POPs with high‐capacity and high‐rate for OCMs.