Flexible lithium selective composite membrane for direct lithium extraction from high Na/Li ratio brine

Monovalent selective ion-exchange membranes have been widely used for lithium extraction from brine with a high Mg/Li ratio. However, extracting Li+ directly from raw brine with high Na/Li ratio remains a significant challenge. This study introduces a flexible lithium selective composite membrane by incorporating lithium-ion conductor with a quaternized polymer. The lithium-ion conductor provides pathways for lithium transmission, while the quaternized polymer effectively hinders the leakage of impurity cations. As a result, with the applied voltage of 2.0 V, the membrane achieved a high Li+/Na+ separation coefficient of 35.48 with a Li+ flux of 8.33 × 10−10 mol cm−2 s−1 in the simulated Yiliping brine, which are 56.3 and 2.8 times higher than that of commercial monovalent selective cation exchange membrane (CIMS). We proposed a lithium transport mechanism involving an adsorption-dehydration-diffusion process through the membrane. Theoretical calculations indicate that the combined effects of significant adsorption energy (−0.47 eV), low dehydration energy (515 kJ mol−1), and low diffusion barrier (0.37 eV) leads to the high selectivity for lithium. These findings provide promising prospects for the large-scale preparation of lithium ion-selective membranes, enabling the direct lithium extraction from raw brine. [Display omitted] •A flexible composite membrane with high lithium selectivity is prepared.•Li0.33La0.56TiO4 facilitates selective pathways for lithium transport.•Quaternized polymer offers a flexible framework and prevents impurity cations leakage.•The membrane achieved a high the Li+/Na+ separation coefficient of 35.48 in the simulated brine.•The membrane shows prospect in the direct lithium extraction by ED process.