Organophosphine‐Functionalized Nitrogen‐Rich Porous p‐Type Polymer Electrode for Li‐Dual‐Ion Batteries

ABSTRACT Organic p‐type polymer cathodes hold great promise for high‐voltage Li‐based dual‐ion batteries (Li‐DIBs), but strong intermolecular aggregation severely hinders anion transport, leading to poor rate capability and cyclability. Herein, we report a novel molecular engineering strategy, incorporating triphenylphosphine (TPP) units into conjugated microporous polymers (CMPs) to construct an amorphous p‐type electrode P(PZ2TPA‐TPP) with hierarchical micro‐mesoporosity and N/P dual redox‐active centers. By virtue of the atomic structural features of phosphine, it embeds highly twisted motifs into the 3D CMP framework to create ample interstitial voids for accelerated PF ₆ ⁻ diffusion, while enhancing intrinsic electron delocalization and anion‐binding affinity. As a proof of concept, the advantages of the organophosphine functionalization strategy were systematically corroborated via electrochemical performance comparison with the nitrogen‐doped counterpart P(PZ2TPA‐TPA). Specifically, P(PZ2TPA‐TPP) exhibits outstanding electrochemical properties, including ultra‐fast charging capability and 100% capacity retention over 100 days under −20 °C low‐temperature conditions. For practical P(PZ2TPA‐TPP)//graphite Li‐DIBs with high areal loading (>10 mg cm ⁻² , 80 wt.% active material), the battery delivers an areal capacity of 1.41 mAh cm ⁻² and sustains stable cycling for 600 cycles. Comprehensive mechanistic investigations verify sequential redox reactions at N/P dual centers, unveiling the unique role of P‐enriched extra sites in anion immobilization and high‐voltage performance improvement.