Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2

Abstract

Supercritical CO₂ (scCO₂) extraction assisted by complexing copolymers is a promising process to recover valuable metals from lithium-ion batteries (LIBs). CO₂, in addition to being non-toxic, abundant and non-flammable, allows an easy separation of metal-complexes from the extraction medium by depressurization, limiting the wastewater production. In this study, CO₂-philic gradient copolymers bearing phosphonic diacid complexing groups (poly(vinylbenzylphosphonic diacid-co-1,1,2,2-tetrahydroperfluorodecylacrylate), p(VBPDA-co-FDA)) were synthesized for the extraction of lithium and cobalt from LiCoO₂ cathode material. Notably, the copolymer was able to play the triple role of leaching agent, complexing agent and surfactant. The proof of concept for leaching, complexation and extraction was achieved, using two different extraction systems. A first extraction system used aqueous hydrogen peroxide as reducing agent while it was replaced by ethanol in the second extraction system. The scCO₂ extraction conditions such as extraction time, temperature, functional copolymer concentration, and the presence of additives were optimized to improve the metals extraction from LiCoO₂ cathode material, leading to an extraction efficiency of Li and Co up to ca. 75 % at 60 °C and 250 bar.

Keywords: Cobalt; Complexing polymers; Critical metals; LIB recycling; Lithium; Supercritical CO(2).