Green and efficient recycling method for spent Ni-Co-Mn lithium batteries utilizing multifunctional deep eutectic solvents.

Given the growing volume of discarded lithium-ion batteries (LIBs), the extraction and recovery of valuable metals through environmentally-friendly solvent processes have become crucial, but they remain challenging tasks. Deep eutectic solvent (DES), an innovative and green solvents, have demonstrated significant promise in the extraction of valued metal elements from spent LIBs. This work employed a multifunctional DES based on natural molecules dimethyl-beta-propiothetin (DMPT) and ethylene glycol (EG) for the efficient leaching of transition metal ions. Under the reduction effect of EG and the action of carboxyl groups and chloride ions in DMPT, the leaching rate of Li, Ni, Co, and Mn can reach 99.59%, 99.28%, 99.04%, and 99.45%, respectively. Furthermore, DFT calculations were employed to explore the microstructure of DES and its interactions with metal ions. The main active site in the DES molecule is near the chloride ion, and DES binds most strongly to Mn, followed by Co, and weakest to Ni. This work avoids the use of volatile acids and demonstrates great potential in extracting valuable metals, providing a sustainable and environment-friendly alternative for the efficient recycling of waste LIBs.

Recycling of waste lithium-ion batteries via a one-step process using a novel deep eutectic solvent.

Deep eutectic solvents (DESs) possess excellent solubility and selectivity, making them suitable for extracting valuable metals and serving as a green alternative in the recycling process. This work introduces a low-viscosity DES consisting of dimethylthetin, oxalic acid, and water for the comprehensive recovery of cathode materials from LIBs. Leaching parameters such as ratio (1:1), leaching temperature (60 °C), and reaction time (15 min) for were systematically optimized, resulting in a selective separation efficiency of 99.98 % for lithium ions. Furthermore, in-situ regeneration of the precursor can be achieved during the leaching process. Charge-discharge tests indicate that the initial charge and discharge capacities of the regenerated battery are 166.8 mAh/g and 138.4 mAh/g, respectively. The DES demonstrates stability and can be easily recycled by replenishing the consumed components. This proposed strategy facilitates the reintroduction of nonrenewable resources into the supply chain and reduces the environmental impact of heavy metals, aligning with the principles of a circular economy.

Hydrophobic Flocculation of Fine Cassiterite Using Alkyl Hydroxamic Acids with Different Carbon Chain Lengths as Collectors.

This work investigated the hydrophobic flocculation of cassiterite using four alkyl hydroxamic acids with varying carbon chain lengths, i.e., hexyl hydroxamate (C6), octyl hydroxamate (C8), decyl hydroxamate (C10) and dodecyl hydroxamate (C12), as collectors. Microflotation tests were performed to investigate the flotation behaviour of cassiterite in the presence of the four alkyl hydroxamic acids. Focused beam reflectance measurement (FBRM) and a particle video microscope (PVM) were used to analyse and monitor the real-time evolution of the particle size distribution of cassiterite and the images of flocs during flocculation. The extended DLVO theory interaction energies between the cassiterite particles were calculated on the basis of the measured contact angle and the zeta potential of cassiterite to determine the aggregation and dispersion behaviour of the cassiterite particles. The microflotation test results suggested that the floatability of cassiterite improved with the increase in the carbon chain length of hydroxamates. FBRM, PVM images and extended DLVO theory calculation results indicated that when C6 was used as the collector, the cassiterite particles could not form hydrophobic flocs because the total potential energy between them was repulsive. When C8, C10 and C12 were used as collectors, the energy barrier amongst particles decreased with increasing hydroxamate concentration. The lowest concentrations of C8, C10 and C12 that could cause the hydrophobic aggregation of cassiterite were approximately 1 × 10-3, 1 × 10-4 and 2 × 10-5 mol/L, respectively. The aggregation growth rate and apparent floc size increased with an increasing collector concentration. Hydroxamic acid with a longer carbon chain could induce the cassiterite particles to form larger flocs at a lower concentration in a shorter time.

Extraction of precious metals from used lithium-ion batteries by a natural deep eutectic solvent with synergistic effects.

As the demand for lithium-ion batteries rises, the growing quantity of waste produced from lithium-ion battery electrode materials becomes an issue of concern. We propose a novel approach for effectively extracting precious metals from cathode materials that address the problem of secondary pollution and high energy consumption that arise from the conventional wet recovery process. The method employs a natural deep eutectic solvent (NDES) composed of betaine hydrochloride (BeCl) and citric acid (CA). The leaching rates of manganese (Mn), nickel (Ni), lithium (Li), and cobalt (Co) in cathode materials may reach 99.2 %, 99.1 %, 99.8 %, and 98.8 %, respectively, due to the synergy of strong coordination ability (Cl-) and reduction (CA) in NDES. This work avoids the use of hazardous chemicals while achieving total leaching in a short period (30 min) at a low temperature (80 °C), achieving an efficient and energy-saving aim. It reveals that NDES has a high potential for recovering precious metals from cathode materials and offers a viable, environmentally friendly method of recycling used lithium-ion batteries (LIBs).

High-efficiency recycling of spent lithium-ion batteries: A double closed-loop process.

Due to the scarcity of raw materials and negative environmental effects, it is essential to selectively recover lithium and other transition metals from end-of-life lithium-ion batteries (LIBs). Here, we propose a dual closed-loop process for resource utilization of spent LIBs. As an alternative to strong inorganic acids, deep eutectic solvents (DESs) as green solvents are employed for the recycling of spent LIBs. The DES based on oxalic acid (OA) and choline chloride (ChCl) achieves efficient leaching of valued metals within a short time. Through the coordination adjustment of water, it can form high-value battery precursors directly in DES, changing wastes into valuables. Meanwhile, water as a diluent can achieve the selective separation of lithium ions via filtration. More importantly, DES can be perfectly re-generated and recycled many times, indicating that the process is cost-effective and eco-friendly. As experimental proof, the re-generated precursors were used to produce new Li(Ni0.5Co0.2Mn0.3)O2 (NCM523) button batteries. The constant current charge-discharge test revealed that the initial charge and discharge values of the re-generated cells were 177.1 and 149.5 mAh/g, respectively, corresponding to the performance of commercial NCM523 cells. The whole recycling process is clean, efficient, and environment-friendly, realizing the double closed loop of spent battery regeneration and deep eutectic solvent re-use. This fruitful research demonstrates DES has excellent potential for recycling spent LIBs and provides an efficient and eco-friendly double closed-loop solution for the sustainable re-generation of spent LIBs.

Effects of Sodium Alginate on the Flotation Separation of Molybdenite From Chalcopyrite Using Kerosene as Collector.

In this paper, the effect of sodium alginate (SA) on the flotation separation of molybdenite (MoS2) from chalcopyrite using kerosene as collector was systematically investigated. The results of single-mineral micro-flotation tests indicated that SA exhibited strong depression on chalcopyrite flotation while it imposed no impact on the floatability of molybdenite. However, in the chalcopyrite-molybdenite mixed-mineral flotation system, the presence of chalcopyrite significantly increased the depressing effect of SA on molybdenite flotation, leading to a considerable reduction in the flotation selectivity. The negative impact of chalcopyrite on the performance of SA in molybdenite flotation was eliminated by adding a certain dosage of kerosene prior to SA. A concentrate containing 53.43% of molybdenum (Mo) was obtained at 76.90% of recovery using 19 mg/L kerosene and 40 mg/L SA at pH 5.4. Zeta potential measurements indicated that the adsorption of SA on chalcopyrite surfaces was stronger than that on molybdenite surfaces, which agreed with the single-mineral flotation test results. The adsorption of SA on chalcopyrite was further confirmed to be chemisorption by Fourier-transform infrared spectroscopy (FTIR) spectra analyses. When Cu2+ appeared in solution, the flotation of molybdenite was strongly depressed by SA. Mechanism analyses indicated that more active sites were generated on molybdenite surfaces after the addition of Cu2+, thus promoting the adsorption of SA.

The role of bulk micro-nanobubbles in reagent desorption and potential implication in flotation separation of highly hydrophobized minerals.

Micro-nanobubbles (MNBs) generated during hydrodynamic cavitation (HC) have been extensively studied in mineral processing field in the past two decades. Many researchers have claimed that MNBs can effectively promote the collection of fine particles in flotation, while studies on MNBs assisted mineral separation are rare. In this study, the role of bulk MNBs in desorbing flotation reagent was investigated, with the aim of illustrating the potential effects of MNBs on minerals separation. The results showed that bulk MNBs could efficiently remove the sodium oleate (NaOl) from diaspore surfaces, reducing the residual concentration of NaOl on solids, which was more significant when the amount of NaOl pre-adsorbed was relatively small. Furthermore, lower residual concentration of NaOl on solids caused by MNBs cleaning made the particles less hydrophobic and flocs more friable. Given that gangue entrapment in flocs was one of the main limits for high-selective flotation, the roles of MNBs in enhancing reagent desorption and associated flocs breakup and reorganization probably contribute to higher separation efficiency of different minerals, which was confirmed by the flotation results of diaspore/kaolinite mixture.

Flotation Separation of Diaspore and Kaolinite by Using a Mixed Collector of Sodium Oleate-Tert Dodecyl Mercaptan.

Sodium oleate (NaOl), a collector in diaspore flotation, has been widely used for more than 30 years, while its low selectivity becomes an issue under today's process requirement. This study introduced tert dodecyl mercaptan (TDM) together with NaOl as a mixed collector to improve selectivity in diaspore flotation. We found that using the mixed collector of NaOl/TDM (total concentration 0.1 mM, the molar ratio 8:2 of NaOl: TDM) at pH = 9-10 significantly effectively separated diaspore and kaolinite. Comparing the recovery of Al2O3 and the ratio of Al2O3 to SiO2 (A/S) treated by NaOl/TDM (pH = 9) and NaOl (pH = 10), the Al2O3 recovery and A/S in concentrate for NaOl/TDM are 7.5% and 2.2 higher than that for NaOl in mixed mineral flotation. Also, surface tension measurements, Zeta potential measurements and Fourier Transform Infrared (FTIR) spectra analysis were used to examine its selectivity from a flotation mechanical perspective. Surface tension measurements show that mixed collector NaOl/TDM has stronger surface activity and hydrophobic association than NaOl. The results of Zeta potential measurements and FTIR spectra analysis indicate that NaOl and TDM can selectively co-adsorb diaspore through physical adsorption. Moreover, the adsorption of TDM promotes the adsorption of NaOl on diaspore. However, when NaOl/TDM treats on kaolinite together, TDM can hardly adsorb on mineral surface, nor can it promote the adsorption of NaOl.

Adsorption of bulk nanobubbles on the chemically surface-modified muscovite minerals.

Bulk nanobubbles (NBs) that are produced in the hydrodynamic cavitation (HC) process have been widely applied in mineral flotation for more than a decade, while how bulk NBs interact with minerals in the water-solid interface is still unclear. In this study, the adsorption behaviors of bulk NBs generated in the principle of HC on muscovite surfaces in the presence of dodecylamine (DDA) were investigated. The results show that NBs are likely coated with DDA in aqueous solutions. After attaching with muscovite, bulk NBs can adsorb on the mineral surfaces, probably following the three-contact line pinning theory. The adsorption of NBs increases the surface hydrophobicity of minerals, which can be inferred from the larger contact angles and the better flotation performances obtained in the presence of DDA/NBs. In addition, the adsorption of NBs is thought to be able to prevent the adsorption of DDA on the same space of the solid surfaces, which can be confirmed by the results of zeta potential measurements, contact angle measurements and AFM imaging results.