Incorporating Redox‐Active Hexaazatrinaphthylene into a 2D Conductive Metal–Organic Framework for Robust Sodium‐Ion Batteries

Abstract Two‐dimensional (2D) conductive metal–organic frameworks (cMOFs) hold tremendous promise as anode materials for sodium‐ion batteries (SIBs), owing to their electrical conductivity, porosity, appropriate interlayer spacing that facilitates ion intercalation, and stability in organic electrolytes. Yet, creating cMOFs hosting multiple redox‐active sites remains challenging. This paper reports a hexaazatrinaphthylene (HATN)‐based 2D cMOF, HATN‐O‐Zn, assembled by coordinating redox‐inactive Zn 2+ through bis(dioxolene) linkages. HATN‐O‐Zn forms hexagonal rod‐like crystals with electrical conductivity that promote rapid Na + diffusion and storage. As an anode, this material delivers a high reversible capacity of 319 mAh g −1 at 0.1 A g −1 and retains a capacity of 86 mAh g −1 after 5000 cycles at 1 A g −1 , demonstrating outstanding cycling stability at room temperature. Notably, HATN‐O‐Zn sustains performance at −20 °C, showing an initial capacity of 117 mAh g −1 and 84.4% retention after 200 cycles at 0.1 A g −1 , underscoring stability under harsh conditions. This stability is attributed to the structural robustness provided by redox‐inactive Zn 2+ . Spectroscopic and theoretical analyses reveal that dual redox‐active sites in the HATN moiety and Zn‐bis(dioxolene) linkages facilitate multiple electron transfer. This work highlights the design potential of combining redox‐active ligands with redox‐inactive metal nodes in 2D cMOFs for durable SIB anodes.