Regulation of Electron Delocalization Region in 2D Heteroligand‐Based Copper‐Organic Framework to Enhance NH4+$ \rm {NH_{4}}{^+}$ Charge Storage

Abstract The rechargeable aqueous ammonium ion battery shows great potential in low‐cost energy storage system because of its long life and environmental friendliness. However, most inorganic host materials used in ammonium ion batteries are still limited by slow diffusion kinetics. Herein, it is identified that a 2D heteroligand‐based copper‐organic framework featuring numerous ammonium ion adsorption site in the π‐conjugated periodic skeleton supplies multiple accessible redox‐active sites for high‐performance ammonium storage. Benefitting from the effective regulation of electron delocalization by heteroligand and the inherent hydrogen bond cage mechanism between ammonium ions, the resultant full battery delivers a large specific energy density of 211.84 Wh kg −1 , and it can be stably operated for 12000 cycles at 5 A g −1 for over 80 days. This explanatory understanding provides a new idea for the rational design of high‐performance MOF‐based ammonium ion battery cathode materials for efficient energy storage and conversion in the future.