Fluorinated Covalent Organic Framework-Based Nanofluidic Interface for Robust Lithium-Sulfur Batteries

To realize the practical application of lithium-sulfur (Li-S) batteries, there is a need to inhibit uncontrolled Li deposition by facilitating Li-ion migration, and suppress the irreversible consumption of cathodes by preventing polysulfide shuttling. However, a permselective artificial membrane or interlayer which features fast ion transport but low polysulfide crossover is elusive. Here, we report the design and synthesis of a fluorinated covalent organic framework (4F-COF)-based membrane with a high permselectivity and increased battery lifespan. Combining density functional theory calculation, molecular dynamic simulation, and in situ Raman analysis, we demonstrate that fluorinated COF eliminates polysulfides shutting and dendritic lithium formation. Consequently, Li symmetrical cells demonstrate Li plating/stripping behaviors for 2000 h under 1 mA cm^-2. More importantly, Li-S batteries based on the 4F-COF/PP separator achieve cycling retention of 82.3% over 1000 cycles at 2 C, rate performance of 568.0 mA h g^-1 at 10 C, and an areal capacity of 7.60 mA h cm^-2 with a high sulfur loading (∼9 mg cm^-2). This work demonstrates that functionalizing nanochannels in COFs can impart permselectivity for energy storage applications. © 2023 American Chemical Society.