The increasing demand for lithium-ion batteries (LIBs) and the critical need for lithium make the efficient recycling of secondary resources essential. Synthetic Li-bearing phases, some with lithium contents greater than natural sources (e.g., spodumene), can occur in slags produced by the pyrometallurgical recycling of end-of-life LIBs. This study investigates both the composition of synthetic model slags reproducing LIB recycling and the recovery potential of Li-bearing phases using SEM-based automated mineralogy and batch flotation tests, respectively. In particular, the efficacy of a novel zwitterionic collector, punicine, in contrast to the conventional collector, oleic acid, was evaluated with a focus on recovering Li-aluminate as a key engineered artificial mineral (EnAM). The flotation tests demonstrated that punicine provided a higher degree of selectivity for Li-aluminate over gehlenite, along with improved recovery of fine and well-liberated particles. The enhanced performance is attributed to punicine’s unique frothing properties and phase-specific interactions. Our findings highlight punicine’s significant potential as a collector for lithium-bearing EnAMs to advance lithium recovery from complex slag materials. The applied unique methodology supports the study of reagent regimes in relation to the flotation behavior of EnAM phases and the sustainable recycling of LIBs.

The transition to sustainable energy systems demands efficient recycling methods for critical raw materials like lithium. In this study, we present a new class of pH- and light-switchable flotation collectors based on isomeric derivatives of the natural product Punicine, termed inverse Punicines. These amphoteric molecules were synthesized via a straightforward four-step route and structurally tuned for hydrophobization by alkylation. Their performance as collectors was evaluated in microflotation experiments of lithium aluminate (LiAlO₂) and silicate matrix minerals such as melilite and calcium silicate. Characterization techniques including ultraviolet-visible (UV-Vis), nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopy as well as contact angle, zeta potential (ζ potential) and microflotation experiments revealed strong pH- and structure-dependent interactions with mineral surfaces. Notably, N-alkylated inverse Punicine derivatives showed high flotation yields for LiAlO₂ at pH of 11, with a derivative possessing a dodecyl group attached to the nitrogen as collector achieving up to 86% recovery (collector conc. 0.06 mmol/L). Preliminary separation tests showed Li upgrading from 5.27% to 6.95%. Radical formation and light-response behavior were confirmed by ESR and flotation tests under different illumination conditions. These results demonstrate the potential of inverse Punicines as tunable, sustainable flotation reagents for advanced lithium recycling from complex slag systems.

Five pH- and light-switchable punicine derivatives were investigated as collectors in the flotation of spodumene and quartz. At the natural pH of the minerals, the punicine substituted with a C17 alkyl residue showed the best recovery under daylight (>5000 lux), with values up to 65.0% and 97.8%, and also the highest absolute recovery difference between the two minerals. For pH values of 2 and 12, the punicine collector with a viologen moiety and a C9 alkyl residue shows the best absolute recovery difference, with values of 32.45% and 32.88%, respectively. Studies on the influence of pH, particle size distribution, UV light and darkness, ζ-potential measurements, and IR spectroscopic measurements were carried out to gain insight into the mechanisms.

The pyridinium phenolate punicine is a switchable molecule from Punica granatum. Depending on the pH, punicine exists as a cation, neutral molecule, anion, or dianion. In addition, punicine reacts to light, under the influence of which it forms radical species. We report on three punicine derivatives that possess an adamantyl, 2-methylnonyl, or heptadecyl substituent and on their performance in the flotation of lithium aluminate, an engineered artificial mineral (EnAM) for the recycling of lithium, e.g., from lithium-ion batteries. By optimizing the parameters: pH and light conditions (daylight, darkness), recovery rates of 92% of LiAlO₂ are achieved. In all cases, the flotation of the gangue material gehlenite (Ca₂Al[AlSiO₇]) is suppressed. IR, the contact angle, zeta potential measurements, TG-MS, and PXRD confirm that the punicines interact with the surface of LiAlO₂, which is covered by LiAl₂(OH)₇ after contact to water, resulting in a hydrophobization of the particle. The plasma pretreatment of the lithium aluminate has a significant influence on the flotation results and increases the recovery rates of lithium aluminate in blank tests by 58%. The oxidative plasma leads to a partial dehydratisation of the LiAl₂(OH)₇ and thus to a hydrophobization of the particles, while a reductive plasma causes a more hydrophilic particle surface.