Superhydrophilic All‐pH‐Adaptable Redox Conjugated Porous Polymers as Universal and Ultrarobust Ion Hosts for Diverse Energy Storage with Chemical Self‐Chargeability

Herein, a new fibrous conjugated microporous polymer bearing phenazine species (PNZ-CMP) is reported as a universal and ultrastable electrode to host various mono- and multi-valent charge carriers for diverse aqueous rechargeable cells combining rapid kinetics, ultralong lifespan, and chemical rechargeability. The porous cross-linked structure, interconnected donor-acceptor network, and readily accessible active sites endow PNZ-CMP with highly-reversible redox activity, superhydrophilicity, facile electron transport, high ion diffusion coefficient, and all-pH-adaptability (−1 to 15) in aqueous electrolytes. Thus, adopting PNZ-CMP electrodes enables good compatibility with H+/Li+/Na+/K+/Zn2+/Al3+ ions and fast surface-controlled redox reactions for diverse aqueous battery chemistry. Multiple PNZ-CMP-based full cells show superior electrochemical performance especially ultralong lifespan, e.g., ≈84% capacity retention over 200 days for K+, ≈100% over 127 days for Zn2+, and ≈76% over 47 days for anion-coordinated Al ions, surpassing small molecule counterparts and most previously-reported corresponding systems. The spontaneous redox chemistry of reduced phenazine species with O2 is first explored to render PNZ-CMP with repeatable chemical self-chargeability in four electrolytes. Especially in 0.05 m H2SO4, an accumulative discharge capacity up to 48505 mAh g−1 is achieved via facile self-charging, which can originate from the “reactive antiaromaticity to stable aromaticity” conversion of the redox moieties as revealed by theoretical studies.