Boosted Anion Storage in Arylamine‐Linked Porous Organic Polymers Enabled by p‐π Conjugation for Sodium‐Based Symmetrical Dual‐Ion Full Cells with Low‐Temperature Adaptability

ABSTRACT Boosting the anion storage capacity and electrochemical kinetics of the electrode materials is crucial for developing low‐temperature sodium‐based dual‐ion batteries (SDIBs). Herein, we proposed the strategy of constructing hydroxy‐activated arylamine‐linked porous organic polymers (HA‐AQ‐OH) linked by arylamine moiety as the electrode materials for low‐temperature SDIBs. The arylamine linkages generated during the polymerization process play dual roles as both covalent connecting units and anion coordination centers. Notably, the introduction of hydroxyl groups enhances the p‐π conjugation effect, extends the π‐electron delocalization, promotes anion storage, and improves the electrochemical kinetics. This endows HA‐AQ‐OH cathode with higher specific capacity (205 mAh g −1 at 0.2 A g −1 ) and better rate capability (123 mAh g −1 at 20 A g −1 ), especially a long‐term stability over 2500 cycles at 0.5 A g −1 under the low temperature of −60°C, surpass its counterpart without hydroxyl activation. Notably, the symmetrical all‐organic SDIBs employing HA‐AQ‐OH as both cathode and anode deliver robust cycling stability over 800 cycles at −60°C. The present study offers an innovative material design strategy toward high‐safety, low‐cost all‐organic SDIBs capable of operating under harsh extreme environments.