Regulation of Interfacial Ion Transport via Honeycomb‐Architected Covalent Organic Frameworks for Lithium Metal Batteries

Abstract This study pioneers vertically aligned honeycomb covalent organic framework (HCCOF) on graphene oxide (HCCOF‐GO) through one‐pot colloidal assembly, establishing a paradigm for interface‐engineered 2D heterostructures in lithium metal batteries (LMBs). Mechanistically, the vertical COF alignment via interfacial π–π conjugation preserves intrinsic 1.15 nm hexagonal pores while integrating Go's electron transport capabilities. When deployed as an artificial solid‐electrolyte interphase (ASEI), this architecture demonstrates triple functionalities: i) “lithiophilic” nanopores enabling dendrite‐free Li + flux (migration barrier 0.29 eV), ii) polarized interfaces regulating anion‐solvent coordination, and iii) gradient organic–inorganic solid electrolyte interphase (SEI) formation. The modified anodes achieve record Li + transference number (t Li + = 0.96) with ultra‐long cyclability (>3000 h at 10 mA cm −2 , 10 mAh cm −2 ) and minimal polarization (ΔV = 13 mV). Competitive electrochemical performance across diverse battery configurations confirms practical viability: the HCCOF‐GO@Li‖NCM811 full cell retains 81.1% of its initial capacity after 100 cycles at a practical loading of 4.5 mAh cm −2 . Corresponding pouch cells (368 Wh kg −1 ) maintain 82.3% capacity retention after 40 cycles, while HCCOF‐GO@Li‖LCO cell demonstrates remarkable cycling stability (500 cycles@80.3%) at a high voltage of 4.7 V.