Manipulation of Linked Phosphorus Chemistry to Enhance the Battery Performance of Phenazine‐Based Porous Polymers

Abstract Organic p‐type cathodes have captured increasing attention for lithium‐organic batteries due to their high voltage output. However, because of the low electronic and ionic conductivity, the p‐type organic electrode materials often show sluggish reaction kinetics and hence low capacities and poor cyclability. In this work, three conjugated polymers (Pz‐TPPO, Pz‐TPPS, and Pz‐TPP) based on p‐type phenazine linked with triphenyl phosphine are reported with different chemical modifications of phosphorus atom. Through oxidation and sulfuration of phosphorus atoms, the electron‐accepting property strength is increased, resulting in higher electronic conductivity of Pz‐TPPO and Pz‐TPPS. It is also found that the P═O unit in Pz‐TPPO exhibits stronger Li⁺ coordination, which can bring anions into close proximity to the redox centers, further improving the anion shuttling during charge and discharge. All these lead to the best lithium‐organic battery performance of Pz‐TPPO, such as high voltage output (3.1–3.9 V), high reversible specific capacity (149 mAh g⁻¹ at 0.2 A g⁻¹) and excellent cycle stability. The potential application has also been demonstrated in Pz‐TPPO//graphite full battery. This work provides a novel strategy for designing donor–acceptor (D–A) conjugated polymer by simple phosphorus modification toward high‐performance organic batteries.