Multielectron Redox‐Bipolar Tetranitroporphyrin Macrocycle Cathode for High‐Performance Zinc‐Organic Batteries

Abstract Bipolar organics fuse the merits of n/p‐type redox reactions for better Zn‐organic batteries (ZOBs), but face the capacity plafond due to low density of active units and single‐electron reactions. Here we report multielectron redox‐bipolar tetranitroporphyrin (TNP) with quadruple two‐electron‐accepting n‐type nitro motifs and dual‐electron‐donating p‐type amine moieties towards high‐capacity‐voltage ZOBs. TNP cathode initiates high‐kinetics, hybrid anion–cation 10e − charge storage involving four nitro sites coordinating with Zn 2+ ions at low potential and two amine species coupling with SO 4 2− ions at high potential. Consequently, Zn||TNP battery harvests high capacity (338 mAh g −1 ), boosted average voltage (1.08 V), and outstanding energy density (365 Wh kg −1 TNP ). Moreover, the extended π‐conjugated TNP macrocycle achieves anti‐dissolution in electrolytes, prolonging the battery life to 50,000 cycles at 10 A g −1 with 71.6 % capacity retention. This work expands the chemical landscape of multielectron redox‐bipolar organics for state‐of‐the‐art ZOBs.