High-Performance Crown Ether-Modified Membranes for Selective Lithium Recovery from High Na+ and Mg2+ Brines Using Electrodialysis

The challenge of efficiently extracting Li+ from brines with high Na+ or Mg2+ concentrations has led to extensive research on developing highly selective separation membranes for electrodialysis. Various studies have demonstrated that nanofiltration membranes or adsorbents modified with crown ethers (CEs) such as 2-OH-12-crown-4-ether (12CE), 2-OH-18-crown-6-ether (18CE), and 2-OH-15-crown-5-ether (15CE) show selectivity for Li+ in brines. This study aims to develop high-performance cation exchange membranes (CEMs) using CEs to enhance Li+ selectivity and to compare the performance of various CE-modified membranes for selective electrodialysis. The novel CEM (CR671) was modified with 12CE, 18CE, and 15CE to identify the optimal CE for efficient Li+ recovery during brine electrodialysis. The modification process included polydopamine (PDA) treatment and the deposition of polyethyleneimine (PEI) complexes with the different CEs via hydrogen bonding. Interfacial polymerization with 1,3,5-benzenetricarbonyl trichloride-crosslinked PEI was used to create specific channels for Li+ transport within the modified membranes (12CE/CR671, 15CE/CR671, and 18CE/CR671). The successful application of CE coatings and Li+ selectivity of the modified membranes were verified through Fourier-transform infrared spectroscopy, zeta-potential measurements, and electrochemical impedance spectroscopy. Bench-scale electrodialysis tests showed significant improvements in permselectivity and Li+ flux for all three modified membranes. In brines with high Na+ and Mg2+ concentrations, the 15CE/CR671 membrane demonstrated more significant improvements in permselectivity compared to the 12CE/CR671 (3.3-fold and 1.7-fold) and the 18CE/CR671 (2.4-fold and 2.6-fold) membranes at current densities of 2.3 mA/cm(2) and 2.2 mA/cm(2), respectively. At higher current densities of 14.7 mA/cm(2) in Mg2+-rich brine and 15.9 mA/cm(2) in Na+-rich brine, the 15CE/CR671 membrane showed greater improvements in Li+ flux, approximately 2.1-fold and 2.3-fold, and 3.2-fold and 3.4-fold compared to the 12CE/CR671 and 18CE/CR671 membranes. This study underscores the superior performance of 15CE-modified membranes for efficient Li+ recovery with low energy demand and offers valuable insights for advancing electrodialysis processes in challenging brine environments.