Regulating the Porosity and Bipolarity of Polyimide‐Based Covalent Organic Framework for Advanced Aqueous Dual‐Ion Symmetric Batteries

The all-organic aqueous dual-ion batteries (ADIBs) have attracted increasing attention due to the low cost and high safety. However, the solubility and unstable activity of organic electrodes restrict the synergistic storage of anions and cations in the symmetric ADIBs. Herein, a novel polyimide-based covalent organic framework (labeled as NTPI-COF) is constructed, featured with the boosted structure stability and electronic conductivity. Through regulating the porosity and bipolarity integrally, the NTPI-COF possesses hierarchical porous structure (mesopore and micropore) and abundant bipolar active centers (C═O and C─N), which exhibits rapid dual-ion transport and storage effects. As a result, the NTPI-COF as the electrodes for ADIBs deliver a high reversible capacity of 109.7 mA h g^-1 for Na⁺ storage and that of 74.8 mA h g^-1 for Cl^- storage at 1 A g^-1, respectively, and with a capacity retention of 93.2% over 10 000 cycles at 10 A g^-1. Additionally, the all-organic ADIBs with symmetric NTPI-COF electrodes achieve an impressive energy density of up to 148 W h kg^-1 and a high power density of 2600 W kg^-1. Coupling the bipolarity and porosity of the all-organic electrodes applied in ADIBs will further advance the development of low-cost and large-scale energy storage.