Long‐Cycle Stable Zn2+ Storage in 2D Conductive Metal–Organic Frameworks via Exclusive Ligand Redox Mechanism

Abstract 2D conductive metal–organic frameworks (2D c‐MOFs) have emerged as novel cathode materials in the development of rechargeable aqueous zinc‐ion batteries (ZIBs) because of its integrated multiple redox‐active moieties. However, the redox of the metal nodes usually leads to the collapse of the c‐MOF structure during Zn 2+ insertion/extraction process, thereby curtailing its cycling lifespan. Herein, a triphenylene‐catecholate‐based 2D c‐MOF (Zn‐HHTP) is fabricated by chelating the inactive Zn nodes, endowing the structural stability during charge and discharge processes only through ligand redox. The 1D open channel of Zn‐HHTP facilitates rapid insertion and extraction of zinc ions, thus enabling stable working of ZIBs at high rates. Impressively, Zn‐HHTP as cathode in ZIBs exhibits an ultra‐long cycling stability with capacity retention of 86.6% after 4000 cycles at the current density of 4 A g −1 , exceeding the other MOF‐based cathodes ever reported. Density functional theory (DFT) calculations combined with ex situ X‐ray photo‐electron spectroscopy (XPS) further elucidate the redox mechanism between catechol and benzene ring of HHTP during the successive insertion/extraction of Zn 2+ , due to their comparatively negative electrostatic potentials. This work provides a new strategy to prolong the cycling capability of ZIBs by utilizing the highly active non‐metallic redox moieties in 2D c‐MOFs.