Lithiophilic Covalent Organic Framework as Anode Coating for High‐Performance Lithium Metal Batteries

The growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well‐aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one‐dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF−Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm−2, which can be well retained up to 400 cycles. Meanwhile, the Li‐COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries. We developed a stable polyimide 2D covalent organic framework (COF), which has abundant lithiophilic quinoxaline and phthalimide units within the 1D channels. The COF can serve as an intermediate layer to guide the uniform electrodeposition of lithium ion, leading to the formation of dense and smooth lithium deposition layer in a cylindrical morphology and steady lithium plating/stripping behaviors.