Redox-Active Covalent Organic Frameworks with Nickel–Bis(dithiolene) Units as Guiding Layers for High-Performance Lithium Metal Batteries

Combining the chemistry of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) can bring new opportunities for the design of advanced materials with enhanced tunability and functionality. Herein, we constructed two COFs based on Ni–bis(dithiolene) units and imine bonds, representing a bridge between traditional MOFs and COFs. The Ni–bis(dithiolene)tetrabenzaldehyde as the 4-connected linker was initially synthesized, which was further linked by 4-connected tetra(aminophenyl)pyrene (TAP) or 3-connected tris(aminophenyl)amine (TAA) linkers into two COFs, namely, Ni-TAP and Ni-TAA. Ni-TAP shows a two-dimensional sql network, while TAA is a twofold interpenetrated framework with an ffc topology. They both exhibit a high Brunauer–Emmett–Teller surface area (324 and 689 m2 g–1 for Ni-TAP and Ni-TAA, respectively), a fairly good conductivity (1.57 × 10–6 and 9.75 × 10–5 S m–1 for Ni-TAP and Ni-TAA, respectively), and high chemical stability (a stable pH window of 1–14 for Ni-TAA). When applied in lithium metal batteries as an intermediate layer for guiding the uniform Li electrodeposition, Ni-TAP and Ni-TAA displayed impressive lithiophilicity and high Li-ion conductivity, enabling the achievement of smooth and dense Li deposition with a clear columnar morphology and stable Li plating/stripping behaviors with high Li utilization, which is anticipated to pave the way to upgrade Li metal anodes for application in high-energy-density battery systems.