Enhanced Proton-Selective Hybrid Polybenzimidazole/Perfluorosulfonic Acid Membranes for Acid Recovery from Lithium Battery Leachate Using Electrodialysis

Daniil Golubenko, Dmitrii Petukhov, Raed A. Al-Juboori, Sabu Varghese, Daniel Johnson, Nidal Hilal

Research output: Contribution to journalArticlepeer-review

Abstract

Proton-selective membranes present a promising solution for improving the efficiency and sustainability of acid recovery in the hydrometallurgical recycling of lithium-ion batteries (LIBs). This study introduces a hybrid cation exchange membrane developed by in situ modification of a commercial perfluorosulfonic acid (PFSA) membrane with polybenzimidazole (PBI) for efficient acid recovery using electrodialysis (ED). The modified membranes demonstrated exceptional proton selectivity and stability, achieving selectivity ratios of 770 (H+/Li+) and 606 (H+/Co2+), surpassing reported values in the literature. In 150 min of electrodialysis, the optimum membrane composite (PFSA-113_PBI-3%) achieved up to 80% acid recovery from synthetic leachates containing H+, Li+, Mn2+, Co2+, and Ni2+. Outstanding separation factors of up to 86 for H+/Li+ and 104 for H+/d-Metal2+, alongside a current efficiency of 95%, were also obtained with the optimum membrane. The enhanced proton selectivity was attributed to the hydrogen-bond networks and ionic interactions resulting from salt bridges between PBI and polymer acidic groups from the formation of a PBI/PFSA interpolymer complex. This was confirmed through membrane structural analysis using Raman and FTIR spectroscopy, electron microscopy, and small-angle X-ray scattering. The separation mechanism of the modified membrane was found to resemble that of biological membranes, as confirmed through carefully designed methylation tests.

Original languageEnglish (US)
JournalACS ES and T Engineering
DOIs
StateAccepted/In press - 2025

Keywords

  • acid recovery
  • cation exchange membranes
  • lithium battery recycling
  • polybenzimidazole
  • proton selectivity

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Environmental Chemistry
  • Process Chemistry and Technology
  • Chemical Health and Safety

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