Ultra‐Thin Hydrogen‐Organic‐Framework (HOF) Nanosheets for Ultra‐Stable Alkali Ions Battery Storage

Abstract Organic frameworks‐based batteries with excellent physicochemical stability and long‐term high capacity will definitely reduce the cost, carbon emissions, and metal consumption and contamination. Here, an ultra‐stable and ultra‐thin perylene‐dicyandiamide‐based hydrogen organic framework (HOF) nanosheet (P‐DCD) of ≈3.5 nm in thickness is developed. When applied in the cathode, the P‐DCD exhibits exceptional long‐term capacity retention for alkali‐ion batteries (AIBs). Strikingly, for lithium‐ion batteries (LIBs), at current of 2 A g −1 , the large reversible capacity of 108 mA h g −1 shows no attenuation within 5 000 cycles. For sodium‐ion batteries (SIBs), the related capacity retains 91.7% within 10 000 cycles compared to the initial state, significantly much more stable than conventional organic materials reported previously. Mechanism studies through ex situ and in situ experiments and theoretical density functional theory (DFT) calculations reveal that the impressive long‐term performance retention originates from the large electron delocalization, fast ion diffusion, and physicochemical stability within the ultra‐thin 2D P‐DCD, featuring π‐π and hydrogen bonding stacking, nitrogen‐rich units, and low impedance. The advantageous features demonstrate that rationally designed stable and effective organic frameworks pave the way to utilizing complete organic materials for developing next‐generation low‐cost and highly stable energy storage batteries.