Lithium Extraction Research Articles

Inaccuracy principle and dissolution mechanism of lithium iron phosphate for selective lithium extraction from brines

The electrochemical lithiation/delithiation (ELD) method with the typical active materials being LiFePO4 and LiMn2O4, is the next generation technique for the selective lithium extraction from slat-lake brines owning to the advantages of high selectivity and excellent capacity and feasibility. However, the dissolution of LiFePO4/FePO4 (LFP/FP) during the ELD is seldom studied and an inaccurate measurement method for dissolution may result in obtaining an incorrect feasible application range for LFP/FP. Here, electrochemical workstation-electrochemical quartz crystal microbalance (EW-EQCM) is first utilized in the brine system to acquire the in-situ dissolution behavior of LFP/FP redox couple and verify the inaccuracy principle of the dissolution measurement. Both experimental results and thermodynamic calculations demonstrated that the accurate dissolution ratios can only be obtained by iron ions and phosphates at pH < 2.7 and pH < 5.3, respectively, which is induced by the narrow soluble range of iron ions and the formation of Ca5(PO4)3OH and Mg3(PO4)2 precipitation. In addition, the stable pH range of LFP and FP is 4 to 10 and 3 to 5, respectively, and the dissolution is caused by the formation of thermodynamically more stable metal ions, metal ion complexes, and metal ion hydroxides. At the optimum pH, the capacity can maintain 35 mg/g with average dissolution ratios of the cathode and anode lower than 0.1 %. This research sheds light on the accurate dissolution measurement range and method, dissolution mechanism and feasible application range of the LFP/FP redox couple.

Lithium extraction from brine through a decoupled and membrane-free electrochemical cell design.

The sustainability of lithium-based energy storage or conversion systems, e.g., lithium-ion batteries, can be enhanced by establishing methods of efficient lithium extraction from harsh brines. In this work, we describe a decoupled membrane-free electrochemical cell that cycles lithium ions between iron-phosphate electrodes and features cathode (brine) and anode (fresh water) compartments that are isolated from each other yet electrochemically connected through a pair of silver/silver-halide redox electrodes. This design is compatible with harsh brines having magnesium/lithium molar ratios of up to 3258 and lithium concentrations down to 0.15 millimolar, enabling the production of battery-grade (>99.95% pure) lithium carbonate. Energy savings of up to ~21.5% were realized by efficiently harvesting the osmotic energy of the brines. A pilot-scale cell with an electrode surface area of 33.75 square meters was used to realize lithium extraction from Dead Sea brine with a recovery rate of 84.0%.

VARIOUS WAYS OF EXTRACTION OF LITHIUM FROM SPODUMENE

This article provides an extensive review of the current advances in the extraction of lithium from spodumene concentrates, a key aspect in the development of this important resource. The article begins with a detailed description of the chemical and physical properties of β-spodumene, particularly emphasizing its importance to the lithium extraction process. The focus is on a variety of methods for processing spodumene, including techniques such as thermal treatment, acid and alkali leaching, as well as more innovative approaches such as solvent utilization and ion exchange.The article highlights not only the technical aspects of each technique, but also their economic and environmental sustainability. Particular attention is paid to the environmental and economic challenges associated with lithium extraction, including the desire to minimize waste and improve overall efficiency. The authors also critically analyze existing limitations such as high costs and process scaling difficulties.An important part of the article is a review and comparison of various research and experimental works in this field, with an emphasis on those that have successfully moved from laboratory studies to realworld applications. The current state of research in lithium extraction is discussed and potential directions for future research are highlighted. Emphasis is placed on the need to further develop and integrate these techniques in the context of sustainable development and efficient resource utilization.

Solar transpiration-powered lithium extraction and storage.

Lithium mining is energy intensive and environmentally costly. This is because lithium ions are typically present in brines as a minor component mixed with physiochemically similar cations that are difficult to separate. Inspired by nature's ability to selectively extract species in transpiration, we report a solar transpiration-powered lithium extraction and storage (STLES) device that can extract and store lithium from brines using natural sunlight. Specifically, the device uses a hierarchically structured solar transpirational evaporator to create a pressure gradient, which allows for the extraction of lithium from brines through a membrane and its storage in a vascular storage layer. Long-term experiments, various membrane tests, and different size assessments demonstrate the stability, compatibility, and scalability of STLES. This solar-powered mining technology provides an alternative developing pathway toward the sustainable extraction of critical resources.

Salar de Atacama Lithium and Potassium Productive Process

The average lithium content in the Earth’s crust is estimated at about 0.007%. Despite this, lithium is considered abundant and widely distributed, with significant extraction from various sources. Notably, the brines in the Salar de Atacama are highlighted for their high lithium concentration ~1800 mg/L. Lithium is currently recovered from these brines through a solar evaporation process. The brine is transferred through a series of ponds, increasing the lithium concentration from 0.2% to 6% over 18 months, while decanting other minerals like potassium, magnesium, and boron. This method is the most efficient and cost-effective globally due to the Salar de Atacama’s high lithium concentration of approximately 1800 ppm and the region’s intense solar radiation, which facilitates evaporation at no economic cost. This manuscript describes in detail the lithium and potassium extraction processes used in the Salar de Atacama.

Advanced lithium extraction nanofiltration membrane with fast transport channels via competitive diffusion and reaction of rigid electropositive phenylbiguanide molecules

The utilization of nanofiltration membranes for lithium extraction from Salt-Lake holds the potential to address lithium resource scarcity and drive energy transformation. Nevertheless, the trade-off effect between water permeability and Mg2+/Li+ separation selectivity poses a challenge in the application of these membranes. In this work, rigid-flexible interpenetration and competitive diffusion reaction strategies were proposed to regulate the pore structure and charge density of the functional layer, thus enhancing the overall separation performance of nanofiltration membrane. Phenylbiguanide (PBG) possessing rigid structure, high positive charge density, and low energy transfer barrier was embedded into flexible polyethyleneimine-based polyamide network. This integration facilitated the formation of continuous and semi-permanent microcavities with rigid-flexible coupled structure, and meanwhile, elevated the density of positive charges. Consequently, the modification extended the water molecular transport channels within the functional layer, leading to a notable enhancement in pure water flux, from 7.40 to 26.43 L m−2h−1. In addition, due to the faster diffusion of PBG than polyethyleneimine with high molecular weight (70000 Da, as aqueous monomer in this work), it could react with excess 1,3,5-trimesoyl chloride (TMC) on the surface of initial membrane to form a new polyamide layer, which repaired the defects in the functional layer and also enhanced the charge density inside pore channels. Therefore, Mg2+/Li+ separation selectivity factor increased from 3.79 of TFC membrane to 22.98 of PBG membrane, i.e., by about 6 times. This study provided an effective strategy to develop nanofiltration membranes with both good water permeability and Mg2+/Li+ selectivity.

A comparative study of discharging and leaching of spent lithium-ion battery recycling

Accelerated production of lithium-ion batteries (LIBs) implies an increase in the raw materials demand, especially for metals like lithium, cobalt, and nickel. Spent LIBs recycling guarantees the regeneration and reincorporation of valuable materials into the manufacturing industry; therefore, recycling methods and techniques must be optimized. In this investigation, alkaline and reductive acid leaching processes were evaluated and compared in order to determine the effect of parameters such as pH, temperature, and reagents concentrations to achieve selective leaching processes. This study demonstrated that strongly alkaline solutions (NaOH) do not ensure selective lithium and aluminum dissolution. Also, a solid compound, LiAl2(OH)6OH(s) can be formed at pH ∼14, negatively affecting the lithium extraction. On the other hand, reductive acid leaching, with acid sulfuric and hydrazine sulfate (H2SO4 + N2H6SO4) solutions resulted in an efficient system, extracting ≥90 % of Ni, Co, and Mn at 40 °C. Hydrazine is essential as a reductant, although it must be added in excess (40 % excess with respect to the Co, Ni, and Mn content) to suppress copper dissolution. Furthermore, this work demonstrated the possibility of processing the entire spent LIBs sample once the discharge and crushing stages were concluded, avoiding physical separation, without affecting the leaching efficiency and contributing to process economy.

Inorganic porous carbon as the supporter of H2TiO3 via in-situ polymerization synchronous conversion for lithium recovery from aqueous solutions

The extraction of lithium from liquid minerals, such as salt lake brines and underground brines, has garnered extensive interest due to its eco-friendly and cost-effective properties. However, the effectiveness of this method is constrained by the stability and capacity of the materials. Herein, a new-type inorganic carbon-supported H2TiO3 adsorbent was developed by a novel in-situ polymerization synchronous conversion strategy. It was found that when resorcinol and formaldehyde containing Li2CO3 and TiO2 were polymerized in-situ and then calcined at 973.15 K, the resin was successfully carbonized to obtain the carbon supporter with a low degree of disorder, and the Li2CO3 and TiO2 in the supporter were synchronously converted into Li2TiO3 and uniformly dispersed in the carbon matrix. Because of the large specific surface area and strong hydrophilicity of the carbon supporter, the material exhibited a maximum Li+ adsorption capacity of 52.14 mg·g−1, which was far higher than that of inorganic composite materials reported at present. Even the equilibrium adsorption capacity for Li+ at a low concentration of 29.26 mg·L−1 reached 28.51 mg·g−1. Following adsorption, the Li+ in the material was easily eluted by 0.25 mol·L−1 HCl, and the elution rate was more than 90 % within 2 h. Dynamic adsorption using a fixed-bed was also performed at 298.15 and 343.15 K, and the adsorption capacity for the same concentration of Li+ was 7.08 and 9.44 mg·g−1, respectively. Because of the high capacity for low-concentration Li+ and the promoting effect of temperature on adsorption, the material is well-suited for recovering Li+ from liquid resources, particularly from geothermal water with high temperatures and low Li+ concentrations.

Novel polyamide nanofiltration membrane PEI-(β-CD@g-C3N5)/TMC based on microfiltration substrate for efficient separation of lithium and magnesium

With the development of industry, the scarcity of lithium resources is becoming increasingly prominent. Therefore, the development of high-performance nanofiltration (NF) membranes for lithium extraction from salt lakes has become crucial. Herein, β-Cyclodextrin (β-CD) and amino-rich graphitic carbon nitride (g-C3N5) sol were uniformly mixed to form β-CD@g-C3N5, which was then mixed with polyetherimide (PEI) monomer and subjected to interfacial polymerization (IP) reaction with trimesoyl chloride (TMC) on a 0.22 μm microfiltration (MF) membrane to prepare the PEI-(β-CD@g-C3N5)/TMC composite NF membrane. Through thin plate theory and gradient operation pressure filtration tests, it was found that the composite NF membrane prepared on the MF membrane substrate was not only defect-free but also exhibited superior compression resistance. In Li+/Mg2+ filtration tests, the PEI-(β-CD@g-C3N5)/TMC membrane showed superior NF performance, with a Li+/Mg2+ selectivity coefficient of 38.85 and a permeability of 8.91 L·m−2·h−1·bar−1. This was attributed to the effect of β-CD@g-C3N5, which could thin the separation layer, slightly enlarge and more uniformly distribute the pores, increase hydrophilicity, and enhance positive charge; meanwhile, the cavity structure provided by β-CD helped to effectively separate Li+/Mg2+. Furthermore, under conditions of mixed salt solutions with different Mg2+/Li+ mass ratios and 80 h of continuous filtration, the membrane exhibited excellent stability. This work introduces innovative membrane materials and design concepts to the field of lithium extraction via NF, potentially paving the way for the industrial application of NF technology.

Enhanced Lithium Extraction from Brines: Prelithiation Effect of FePO4 with Size and Morphology Control.

Extracting lithium resources from seawater and brine can promote the development of the new energy materials industry. The electrochemical method is green and efficient. Iron phosphate (FePO4) crystal, with its 1D ion channel, holds significant potential as a primary lithium extraction electrode material. Li+ encounters a substantial concentration disadvantage in brines, and the co-intercalation of Na+ diminishes Li+ selectivity. To address this issue, this work enhances the energy barrier for Na+ insertion through prelithiation strategies applied to the 1D channels of FePO4 crystal, thereby improving Li+ selectivity, and further investigating the prelithiation effect with particle size and morphology control. The results indicate that the Li(4C-40%)FePO4// Activated carbon(AC) system enhances selectivity of lithium. The Li(4C-40%)FePO4 with size diameter of 2500nm demonstrates an energy consumption of 0.79Whmol-1 and a purity of 97.94% for lithium extraction at a unit lithium extraction of 5.93mmolg-1 in simulated brine. Li(4C-40%)FePO4-nanoplates demonstrate the most optimal lithium extraction performance among the three morphologies due to their lamellar structure's short ion diffusion path in the [010] channel, favoring Li+ diffusion. The diffusion energy barriers of Li+ and Na+ are calculated using Density Functional Theory (DFT) before and after prelithiation, showing good agreement with experimental results.

Triple synergistic effects of bismuth doping in spinel-LiMn2O4: A path to high-performance electrochemical lithium extraction from salt-lake brine

The electrochemical extraction of lithium-ion from salt-lake brine has attracted significant global interest due to the rising requirement for lithium resources. The electrochemical extraction system based on LiMn2O4 has emerged as one of the most promising methods for commercial lithium extraction. However, the dissolution of manganese in LiMn2O4 material, caused by the Jahn-Teller effect, poses a significant obstacle to achieving large lithium extraction capacity and long lifespan simultaneously. In this study, we addressed the issue by incorporating Bi3+ into the material. The resulted LMBO material displays a truncated octahedral morphology, with {100} crystal faces facilitating Li+ diffusion. Additionally, Bi3+-doping inhibits the Jahn-Teller effect and expands the Li+ diffusion pathway, thereby, enhancing the stability and Li+ diffusion rate of LMO. In particular, LMBO-2 material exhibits an excellent lithium ion diffusion rate of 2.03 × 10−9 cm2·s−1, and demonstrates outstanding Li+ release efficiency, which reaches 26.46 mg·g−1 per cycle with an average energy consumption of 2.04 Wh·mol−1 in the 30 mmol⋅L−1 simulated salt-lake brine. In simulated Zabuye brine solution, LMBO//Ag system displayed an admirably release capacity of 26.17 mg·g−1 characterized by an ultra-low Li/Na ratio, with Li/Na ratio in recovery solution reaching as high as 0.54. These significant findings advance practical applications of LiMn2O4 in brine lithium extraction processes.

Selective recovery of lithium from used lithium-ion batteries spent via grain boundary reconstruction reaction

The demand for lithium resources on the market has increased significantly as a result of the emergence and advancement of the new energy industry. However, improper handling leads to the generation of large amounts of hazardous waste, including spent lithium batteries. The recovery of lithium from these batteries has dual importance in protecting the environment and effectively recycling secondary resources. Herein, a green process for selective extraction of lithium from discarded lithium batteries was proposed. Sodium thiosulfate mixed with waste lithium battery powder was calcined at 600 °C for 90 min, when the molar ratio of sodium thiosulfate to lithium in the raw material was 0.5, and over 99 % lithium can be selectively preferentially extracted. During the roasting process, lithium in the raw materials was converted into water-soluble LiNaSO4, and transition metal oxides after calcination existed as water-insoluble oxides or sulfides, and the goal of preferential lithium extraction can be achieved by simple immersion in water. Lithium-containing leachate was purified by cerium carbonate and NaOH. After removing a small amount of Ni, Co, Mn, Al, Ca, and F impurities, the prepared lithium carbonate had a purity greater than 99.50 %, which met the standard of battery-grade lithium carbonate. This study introduces an approach to the selective extraction of lithium from lithium-containing solid waste, which effectively simplifies the recycling separation procedure and provides support for resource utilization of lithium-containing solid waste.

Space-Confined Synthesis of Thinner Ether-Functionalized Nanofiltration Membranes with Coffee Ring Structure for Li+/Mg2+ Separation.

Positively charged nanofiltration membranes have attracted much attention in the field of lithium extraction from salt lakes due to their excellent ability to separate mono- and multi-valent cations. However, the thicker selective layer and the lower affinity for Li+ result in lower separation efficiency of the membranes. Here, PEI-P membranes with highly efficient Li+/Mg2+ separation performance are prepared by introducing highly lithophilic 4,7,10-Trioxygen-1,13-tridecanediamine (DCA) on the surface of PEI-TMC membranes using a post-modification method. Characterization and experimental results show that the utilization of the DCA-TMC crosslinked structure as a space-confined layer to inhibit the diffusion of the monomer not only increases the positive charge density of the membrane but also reduces its thickness by ≈35% and presents a unique coffee-ring structure, which ensures excellent water permeability and rejection of Mg2+. The ion-dipole interaction of the ether chains with Li+ facilitates Li+ transport and improves the Li+/Mg2+ selectivity (SLi,Mg=23.3). In a three-stage nanofiltration process for treating simulated salt lake water, the PEI-P membrane can reduce the Mg2+/Li+ ratio of the salt lake by 400-fold and produce Li2CO3 with a purity of more than 99.5%, demonstrating its potential application in lithium extraction from salt lakes.

Microbial Mineralization with Lysinibacillus sphaericus for Selective Lithium Nanoparticle Extraction.

Lithium is a critical mineral in a wide range of current technologies, and demand continues to grow with the transition to a green economy. Current lithium mining and extraction practices are often highly ecologically damaging, in part due to the large amount of water and energy they consume. Biomineralization is a natural process that transforms inorganic precursors to minerals. Microbial biomineralization has potential as an ecofriendly alternative to current lithium extraction techniques. This work demonstrates Lysinibacillus sphaericus biomineralization of lithium chloride to lithium hydroxide. Quantitative analysis of biomineralized lithium via the 2-(2-hydroxyphenyl)-benzoxazole fluorescence assay reveals significantly greater recovery with L. sphaericus than without. Furthermore, L. sphaericus biomineralization is specific to lithium over sodium. The nanoparticles produced were further characterized via Fourier transform infrared and transmission electron microscopy analysis as crystalline lithium hydroxide, which is an advanced functional material. Finally, ESI-LC/MS was used to identify several proteins involved in this microbial biomineralization process, including the S-layer protein. Through the isolation of L. sphaericus ghosts, this work shows that the S-layer protein alone plays a critical role in the biomineralization of crystalline lithium hydroxide nanoparticles. Through this study of microbial biomineralization of lithium with L. sphaericus, there is potential to develop innovative and environmentally friendly extraction techniques.

A novel technology for lithium extraction through low-temperature synergistic roasting of α-spodumene with lepidolite

α-Spodumene and lepidolite have garnered significant attention because of the booming market of lithium (Li) salts. However, α-spodumene requires a high-temperature phase transition step at ≥1050 °C, and lepidolite needs a large amount of sulfate to extract Li. The economic and environmental benefits of these processes need to be improved. Herein, an innovative scheme, low-temperature synergistic roasting of α-spodumene with lepidolite, was proposed to efficiently extract Li. The conditions for phase transition roasting, acid baking, and water leaching were sequentially optimized. The mechanisms underlying the synchronous phase transition of α-spodumene and lepidolite were studied using various characterization methods. Results indicated that lepidolite lowers the transition temperature of spodumene from the α-phase to the β-phase by 150 °C. During the synergistic roasting, fluorine escapes from the lepidolite lattice and attacks SiO, AlO, and LiO bonds within the α-spodumene lattice. Under optimal conditions, 97.60 % of the Li was extracted, while the leaching ratios of Na, K, Al, and Si were only 50.96 %, 10.96 %, 5.75 %, and 0.30 %, respectively. Current scheme is a promising low-carbon technology that synchronously achieves the low-temperature phase transition of α-spodumene and additive-free Li extraction from lepidolite, offering superior economics, environmental benefits, and practicality compared with the existing methods.

Photothermal-enhanced ion transport for efficient electrochemical lithium extraction at low temperatures

The demand for lithium (Li) resources is booming due to the widespread applications of Li-ion batteries recently. Electrochemically extracting lithium from brines is a promising approach to address the shortage of Li resources. However, when working at low temperatures, which are inevitable in frigid salt lakes, the performance is severely deteriorated due to depressed transport kinetics. Herein, we addressed this issue by constructing a new electrochemical lithium extraction system using polypyrrole-coated FePO4 as the electrode material, which exhibits superior performance at low temperatures due to photothermal effect of polypyrrole. At an ambient temperature of 5 °C and irradiated with sunlight, this system achieved a lithium intercalation capacity of 5.84 mmol g−1 (2.72 times higher than that without solar irradiation) at an extraction rate of 5.92 mmol g−1 h−1 from a 15 mM LiCl solution, and a selectivity of 124 towards Li over Mg. After 5000 cycles of continuous operation, the system still retained 81 % of its initial capacity at a current density of 50 A m−2. The proposed photothermal-enhanced electrochemical lithium extraction system has great application potential for lithium extraction from brine at low-temperature regions.

Effects of size and shape of hole defects on mechanical properties of biphenylene: a molecular dynamics study

The distinctive multi-ring structure and remarkable electrical characteristics of biphenylene render it a material of considerable interest, notably for its prospective utilization as an anode material in lithium-ion batteries. However, understanding the mechanical traits of biphenylene is essential for its application, particularly due to the volumetric fluctuations resulting from lithium ion insertion and extraction during charging and discharging cycles. In this regard, this study investigates the performance of pristine biphenylene and materials embedded with various types of hole defects under uniaxial tension utilizing molecular dynamics simulations. Specifically, from the stress‒strain curves, we obtained key mechanical properties, including toughness, strength, Young's modulus and fracture strain. It was observed that various near-circular hole (including circular, square, hexagonal, and octagonal) defects result in remarkably similar properties. A more quantitative scaling analysis revealed that, in comparison with the exact shape of the defect, the area of the defect is more critical for determining the mechanical properties of biphenylene. Our finding might be beneficial to the defect engineering of two-dimensional materials.

Exploring the thermodynamics and dynamics of lithium ions inserted into Li1-xMn2O4 electrode at different temperatures

Efficient lithium extraction via electrochemical adsorption holds great promise for resource utilization and energy storage. However, the mechanism of how temperature influences the electrochemical adsorption process, particularly the thermodynamics and dynamics in the liquid, liquid–solid interface, and solid remains unclear. To address this challenge, we explored the impact of temperature (273.15 to 328.15 K) using Li1-xMn2O4 as an adsorbent. For the liquid phase, the conductivity increased from 0.89 to 0.95 S/m following lnΛ = -0.11(1000/T) + 0.27 in thermodynamics; the solution viscosity decreased from 1.71 × 10-3 to 5.15 × 10-4 Pa·s conforming lnη = 1.96(1000/T) − 13.54 in dynamics. For the liquid–solid interface, the charge transfer resistance (Rct) decreased from 42.03 to 25.17 ohm obeying ln(1/Rct) = -0.82(1000/T) − 0.69 in thermodynamics; the exchange current (i0) showed a positive correlation with temperature in fitting Logi0 = -0.50(1000/T) − 1.40 in dynamics. For the solid phase, the increase in reduction peak voltage (ERP) and the decrease in Gibbs free energy (G), entropy (S), and enthalpy (H) all indicate that the increase of temperature promotes lithium ions to inserted into Li1-xMn2O4 in thermodynamics; the increased diffusion coefficient (DLi+(S)) and higher reduction peak current (IRP) suggest that higher temperature strengthens lithium ions diffusion and insertion in dynamics. In the temperature range, the adsorption capacity gradually increased from 1.15 to 7.37 mg/g, the initial current enhanced from −3.40 × 10-4 to −1.85 × 10-3 A, the terminal current raised from −1.59 × 10-4 to −7.40 × 10-4 A, and the current efficiency improved from 31.28 % to 66.11 % in the temperature range. This work provides a deeper understanding of the impact of temperature on the electrochemical lithium adsorption process from thermodynamics and dynamics. This work also offers crucial guidance for the upgrading of electrochemical lithium adsorption technology and can be applied to other fields such as energy storage, catalysis, and synthesis, providing a valuable reference for optimizing reaction parameter design in thermodynamics and dynamics.

Enhanced Mg2+/Li+ separation performance of polyelectrolyte multilayers nanofiltration membranes modified by trimethylamine N-oxide zwitterions

Polyelectrolyte multilayer nanofiltration (NF) membranes have garnered attention for their potential in Mg2⁺/Li⁺ separation applications, particularly due to their positively charged nature and the versatility offered by the layer-by-layer (LbL) self-assembly technique. However, these membranes often face significant challenges in balancing high ion selectivity with adequate water permeability. Addressing these limitations, this study introduces a novel approach by grafting a zwitterionic material, trimethylamine N-oxide (TMAO), onto polyacrylamide hydrochloride (PAH), creating a new cationic polyelectrolyte (TPAH). By cyclically depositing sodium polystyrene sulfonate (PSS) and TPAH onto a polyethersulfone (PES) substrate, we have successfully fabricated a high-performance NF membrane (i.e., (PSS/TPAH)n) that demonstrates enhanced Mg2⁺/Li⁺ selectivity with high water permeability. TMAO features shorter distances between its positive and negative charge groups and smaller dipoles compared to other zwitterions. These characteristics enhance its ability to resistance to salt effects and transfer charge from amine oxide to water molecule. Furthermore, the grafting of TMAO enhanced the hydrophilicity of TPAH and regulated the charge distribution of the polyelectrolyte. Compared to the control membrane (PSS/PAH)n, the optimized membrane (PSS/TPAH)n showed reduced rejection of LiCl from 60.9 ± 2.7 % to 35.9 ± 1.5 %, while that of MgCl2 increased from 94.3 ± 1.6 % to 96.1 ± 0.7 %. Additionally, water permeability improved from 9.2 ± 0.9 LMH/bar to 16.1 ± 0.5 LMH/bar. Notably, the membranes exhibited an improved selectivity for Mg2+/Li+ ions in synthetic saline, reaching a maximum of 30.5 ± 1.5, highlighting its potential for practical separation applications. Density functional theory simulations indicate that TMAO not only enhances Donnan effect and intensify ion dehydration of polyelectrolyte multilayers NF membranes but also increases their hydrophilicity. In general, these polyelectrolyte multilayers NF membranes exhibit considerable promise for multiple applications, such as seawater pretreatment, groundwater softening and lithium extraction.

Selective leaching of lithium from mixed spent lithium iron phosphate powder

In recent years, lithium iron phosphate (LFP) batteries have been widely used in the electric vehicle industry. The recycling of spent LFP will be propitious to conserving resources and alleviating the environmental risks it poses. In this study, a selective extraction method for lithium from spent LFP was proposed using nitric acid. Lithium leached into the liquid phase, while P and Fe remained in the leaching residue. Under the conditions of 120°C, HNO3/Li molar ratio of 2, and time of 2 h, the leaching efficiency of lithium reached 99.5 %, with a selectivity reaching 82.1 %. Initially, LFP was decomposed to liberate Li, Fe, and P in the liquid phase. Subsequently, ferrous ions were oxidized to trivalent, high-valent iron ions re-precipitated as FePO4·2 H2O. Thermodynamic calculations indicate that the temperature and pH value of the extraction system have significant influence on both the oxidation and reprecipitation steps. An imbalance of Fe/P ratio (<1) in the raw material hinders the selectivity of lithium extraction, and supplementing this portion of Fe can enhance the selectivity to over 90 %. Additionally, LiCO3 and anhydrous FePO4 were effectively regenerated from the leachate and residue. This study provides a novel approach for the recycling of spent LFP and probably contributes to the sustainability of the lithium ion battery industry.