Quaternization-spiro design of chlorine-resistant and high-permeance lithium separation membranes

Abstract

Current polyamide lithium extraction nanofiltration membranes are susceptible to chlorine degradation and/or low permeance, two problems that are hard to reconcile. Here we simultaneously circumvented these problems by designing a quaternized-spiro piperazine monomer and translating its beneficial properties into large-area membranes (1 × 2 m2) via interfacial polymerization with trimesoyl chloride. The quaternary ammonium and spiral conformation of the monomer confer more positive charge and free volume to the membrane, leading to one of the highest permeance (~22 L m−2 h−1 bar−1) compared to the state-of-the-art Mg2+/Li+ nanofiltration membranes. Meanwhile, membrane structures are chlorine resistant as the amine–acyl bonding contains no sensitive N-H group. Thus the high performance of membrane is stable versus 400-h immersion in sodium hypochlorite, while control membranes degraded readily. Molecular simulations show that the high permeance and chlorine resistance, which were reproducible at the membrane module level, arise from the spiral conformation and secondary amine structures of the monomer.