Cation Exchange Membranes Coated with Polyethyleneimine and Crown Ether to Improve Monovalent Cation Electrodialytic Selectivity

Developing monovalent cation permselective membranes (MCPMs) with high-efficient permselectivity is the core concern in specific industrial applications. In this work, we have fabricated a series of novel cation exchange membranes (CEMs) based on sulfonated polysulfone (SPSF) surface modification by polyethyleneimine (PEI) and 4′-aminobenzo-12-crown-4 (12C4) codeposited with dopamine (DA) successively, which was followed by the cross-linking of glutaraldehyde (GA). The as-prepared membranes before and after modification were systematically characterized with regard to their structures as well as their physicochemical and electrochemical properties. Particularly, the codeposition sequence of modified ingredients was investigated on galvanostatic permselectivity to cations. The modified membrane (M-12C4-0.50-PEI) exhibits significantly prominent selectivity to Li+ ions (PMg2+Li+ = 5.23) and K+ ions (PMg2+K+ = 13.56) in Li+/Mg2+ and K+/Mg2+ systems in electrodialysis (ED), which is far superior to the pristine membrane (M-0, PMg2+Li+ = 0.46, PMg2+K+ = 1.23) at a constant current density of 5.0 mA·cm−2. It possibly arises from the synergistic effects of electrostatic repulsion (positively charged PEI), pore-size sieving (distribution of modified ingredients), and specific interaction effect (12C4 ~Li+). This facile strategy may provide new insights into developing selective CEMs in the separation of specific cations by ED.