Three-dimensional covalent organic framework-based artificial interphase layer endows lithium metal anodes with high stability.

To gain a deeper understanding and address the scientific challenges of lithium dendrite growth, a robust solid-state electrolyte interface (SEI) with good mechanical properties and rapid ion conduction is crucial for the advancement of lithium metal batteries. Artificial SEI layers based on organic polymers, such as covalent organic frameworks (COF), have garnered widespread attention due to their flexible structural design and tunable functionality. In this work, a COF with 3D spatial geometric symmetry and a fully covalent topology was synthesized and used as artificial SEI layers. A combination of comprehensive DFT calculations and / characterizations have unraveled the impact of interpenetrated chain segments and anchoring lithiophilic groups on the microscopic dynamics related to Li ion desolvation, charge transfer, migration pathways, and deposition morphology. The ultralow polarization voltage of 46 mV for 9400 hours with a symmetric Li|Li cell at a harsh current density of 10 mA cm, as well as the high Li utilization, low polarization voltage, and prolonged lifespan for 3D-COF-modified Li|S and Li|LFP full cells, unambiguously corroborate the interphase reliability. This work also aims to shed new light on the use of multi-dimensional porous polymer SEI layers to revive highly stable Li metal batteries.