The Influence of the Electrolyte on Lithium Transport Through the DAAQ‐TFP‐COF Structure: A Molecular Dynamics Study

ABSTRACT Covalent organic frameworks (COFs) have emerged as promising electrode materials for lithium‐ion batteries (LIBs) due to their tunable redox‐active properties and environmental benefits. However, the influence of electrolytes on COF‐based battery performance remains poorly understood at the molecular level. In this study, we employ molecular dynamics simulations to investigate the interaction between terephthalaldehyde and 1,3,5‐tris(4‐aminophenyl)benzene COF (DAAQ‐TFP‐COF) and two organic electrolytes: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in tetraethylene glycol dimethyl ether (TEGDME) and LiPF 6 in a mixture of ethylene carbonate and diethyl carbonate (EC/DEC). Our simulations reveal different lithium coordination environments: while LiTFSI in TEGDME shows better salt dissociation, LiPF 6 in EC/DEC exhibits higher lithium self‐diffusion coefficients, despite greater coordination to the COF structure. We identify that lithium transport is primarily mediated by the organic solvent, with COF coordination sites hindering mobility. These findings highlight the importance of electrolyte selection in optimizing COF‐based electrodes for LIBs and provide novel insights into the interplay between structural properties and ionic dynamics in porous frameworks.