A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices

Rechargeable aqueous Zn-ion energy storage devices are promising candidates for next-generation energy storage technologies. However, the lack of highly reversible Zn²⁺-storage anode materials with low potential windows remains a primary concern. Here, we report a two-dimensional polyarylimide covalent organic framework (PI-COF) anode with high-kinetics Zn²⁺-storage capability. The well-organized pore channels of PI-COF allow the high accessibility of the build-in redox-active carbonyl groups and efficient ion diffusion with a low energy barrier. The constructed PI-COF anode exhibits a specific capacity (332 C g⁻¹ or 92 mAh g⁻¹ at 0.7 A g⁻¹), a high rate capability (79.8% at 7 A g⁻¹), and a long cycle life (85% over 4000 cycles). In situ Raman investigation and first-principle calculations clarify the two-step Zn²⁺-storage mechanism, in which imide carbonyl groups reversibly form negatively charged enolates. Dendrite-free full Zn-ion devices are fabricated by coupling PI-COF anodes with MnO₂ cathodes, delivering excellent energy densities (23.9 ∼ 66.5 Wh kg⁻¹) and supercapacitor-level power densities (133 ∼ 4782 W kg⁻¹). This study demonstrates the feasibility of covalent organic framework as Zn²⁺-storage anodes and shows a promising prospect for constructing reliable aqueous energy storage devices.