2D Exfoliation Chemistry Towards Covalent Pseudo‐Layered Phosphate Framework Derived by Radical/Strain‐Synergistical Process

Abstract 2D compounds exfoliated from weakly bonded bulk materials with van der Waals (vdW) interaction are easily accessible. However, the strong internal ionic/covalent bonding of most inorganic crystal frameworks greatly hinders 2D material exfoliation. Herein, we first proposed a radical/strain‐synergistic strategy to exfoliate non‐vdW interacting pseudo‐layered phosphate framework. Specifically, hydroxyl radicals (⋅OH) distort the covalent bond irreversibly, meanwhile, H 2 O molecules as solvents, further accelerating interlayered ionic bond breakage but mechanical expansion. The innovative 2D laminar NASICON‐type Na 3 V 2 (PO 4 ) 2 O 2 F crystal, exfoliated by ⋅OH/H 2 O synergistic strategy, exhibits enhanced sodium‐ion storage capacity, high‐rate performance (85.7 mAh g −1 at 20 C), cyclic life (2300 cycles), and ion migration rates, compared with the bulk framework. Importantly, this chemical/physical dual driving technique realized the effective exfoliation for strongly coupled pseudo‐layered frameworks, which accelerates 2D functional material development.