With the rapid development of 3D printing technologies, more attention has been focused on using 3D printing for the fabrication of membranes. This study investigated the application of digital light processing (DLP) 3D printing combined with quaternization processes to develop dense anion exchange membranes (AEMs) for electrodialysis (ED) separation of Cl− and SO42− ions. It was discovered that at optimal curing times of 40 min, the membrane pore density was significantly enhanced and the surface roughness was reduced, and this resulted in an elevation of desalination rates (97.5–98.7%) and concentration rates (165.8–174.1%) of the ED process. Furthermore, increasing the number of printed layers improved the membranes’ overall polymerization and performance, with double-layer printing showing superior ion flux. This study also highlights the impact of the polyethylene glycol diacrylate (PEGDA) molecular weight on membrane efficacy, where PEGDA-700 outperformed PEGDA-400 in ion transport capabilities and desalination efficiency. Additionally, higher 4-vinylbenzyl chloride (VBC) content improved the quaternary ammonium group concentration and membrane conductivity, and hence elevated the ED performance. Under optimized conditions, DLP 3D printed membranes demonstrated exceptional selectivity of 24.0 for Cl−/SO42− and a selective purity of 81.4%. With a current density of 400 A/m2, the current efficiency and energy consumption were in the range of 82.4% to 99.7%, and 17.2 to 25.4 kW‧h‧kg−1, respectively, showcasing the potential of advanced manufacturing techniques in creating efficient and functional ion exchange membranes.
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