Dehydration‐enhanced Ion Recognition of Triazine Covalent Organic Frameworks for High‐resolution Li+/Mg2+ Separation

The precise and rapid extraction of lithium from salt‐lake brines is critical to meeting the global demand for lithium resources. However, it remains a major challenge to design ion‐transport membranes with accurate recognition and fast transport path for the target ion. Here, we report a triazine covalent organic framework (COF) membrane with high resolution for Li+ and Mg2+ that enables fast Li+ transport while almost completely inhibiting Mg2+ permeation. The remarkably high rejection of Mg2+ by the COF membrane is achieved via imposed ion dehydration and the construction of the energy well. The proper hydrophilic environment of the COF channel promotes the dissociation of Li+ from the negatively charged functional groups, allowing Li+ for hopping transport supported by the sulfonate side‐chains to shorten the diffusion path of Li+. Under high‐salinity electrodialysis conditions, the COF membrane demonstrates robust Li+/Mg2+ separation performance (No Mg2+ were detected in the collected solution), achieving efficient lithium recovery and high product purity (Li2CO3: 99.3%). This membrane design strategy enables high energy efficiency and powerful lithium extraction in the electrodialysis lithium extraction process, and can be generalized to other energy and separation related membranes.