Biomimetic Gourd‐Vine Supramolecular Engineering for High‐Performance Organic Cathode Through Dual‐Mode of Anion Coordination and Conjugated Redox Activation

P-type organic cathode materials feature multielectron redox activity, structural tunability, and elevated redox potentials, making them promising candidates for battery applications. Nevertheless, their practical deployment remains hindered by inherent challenges, particularly the persistent dissolution issue in conventional electrolytes, leading to rapid capacity fading. To overcome these intrinsic limitations, we propose a biomimetic supramolecular engineering strategy inspired by the hierarchical reinforcement observed in gourd-vine systems, which integrates two synergistic design principles. First, the alkyl-based polymeric backbone and π-π stacking impose steric confinement to suppress solvation-driven degradation. Second, the conjugated aryl groups strategically are positioned on the phenazine scaffold to enhance charge delocalization and activate redox-active nitrogen sites. This approach not only endows the battery system with exceptional long-term cycling stability but also enables high-capacity energy storage with sustained operational durability. The resultant 5,10-diaryl-5,10-dihydrophenazine polymer cathode exemplifies this paradigm, demonstrating outstanding electrochemical performance including an impressive reversible capacity of approximately 120 mAh g^-1 at 100 mA g^-1 and an excellent capacity retention of 88% over 2000 cycles, representing one of the most robust performances reported for organic cathodes. Comprehensive characterizations combined with theoretical simulations systematically elaborate a dual-mode charge compensation mechanism involving the reversible anion (de)coordination coupled with conjugated π-electron redox activation.