Layer-by-layer assembly of cation exchange membrane for highly efficient monovalent ion selectivity

The development of cation exchange membranes (CEMs) with high monovalent/divalent cation selectivity has great potential for enhanced salt separation for wastewater reclamation, and layer-by-layer (LbL) self-assembly of polyelectrolyte films with high monovalent selectivities among cations has expanded the applications of such membranes. However, the structure–property relationship for constructing multilayered polyelectrolyte films with enhanced separation performance remains poorly understood. This study reports a novel CEM engineered by coating a [polyethyleneimine/polystyrene sulfonate (PEI/PSS)]n alternate electro-deposition multilayer on a polyacrylate substrate membrane. The newly developed CEM exhibited a monovalent selectivity of 4.59 for Li+/Mg2+ with an optimal permeation of 0.16 mmol·cm−2·h−1 for Li+, demonstrating a competitive separation property compared to state-of-the-art permselective membranes. A detailed quantitative investigation provides the underlying insights into the monovalent selectivity for each polyelectrolyte layer. The results indicate negligible interface impedance toward monovalent cations but strengthened repulsion against divalent cations, thereby promoting a quick passage for monovalent cations while imposing temporal retardation on divalent cations during the electrodialysis (ED) process. Therefore, this study elucidates the characteristic reason for the enhanced monovalent ion permselectivity of LbL polyelectrolyte membranes in electro-driven separation processes.