Olefin‐Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes

Abstract Despite the enormous interest in Li metal as an ideal anode material, the uncontrollable Li dendrite growth and unstable solid electrolyte interphase have plagued its practical application. These limitations can be attributed to the sluggish and uneven Li+ migration towards Li metal surface. Here, we report olefin‐linked covalent organic frameworks (COFs) with electronegative channels for facilitating selective Li+ transport. The triazine rings and fluorinated groups of the COFs are introduced as electron‐rich sites capable of enhancing salt dissociation and guiding uniform Li+ flux within the channels, resulting in a high Li+ transference number (0.85) and high ionic conductivity (1.78 mS cm−1). The COFs are mixed with a polymeric binder to form mixed matrix membranes. These membranes enable reliable Li plating/stripping cyclability over 700 h in Li/Li symmetric cells and stable capacity retention in Li/LiFePO4 cells, demonstrating its potential as a viable cationic highway for accelerating Li+ conduction.