Search Results (43)

Selective ion transport is essential for many applications of membrane separation, such as rare metal and high-value element extraction from complex ionic sources. However, efficient regulation of permeability–selectivity remains a major challenge for advanced ionic transport membranes. Herein, we demonstrate that supercritical CO₂ (ScCO₂) drying combined with crown ether functionalization enables precise modulation of crystallinity and ion-specific affinity in covalent organic framework (COF) membranes. The pristine COF membrane prepared by solution casting was amorphous. Owing to its positively charged framework and sub-nanometer pores, the membrane exhibited a high Li⁺ transport rate over Mg²⁺ via a synergistic effect of size exclusion and electrostatic repulsion, resulting in a selectivity of 204. After ScCO₂ drying, the crystallinity and structural ordering of the COF membrane were significantly enhanced, leading to a 1.5-fold increase in Li⁺ flux, accompanied by a moderate decrease in selectivity to 147. To compensate for this trade-off, 12-crown-4 (12C4) was introduced as a Li⁺ recognition agent into the ScCO₂-treated membrane, restoring Li⁺/Mg²⁺ selectivity to 187 without compromising Li⁺ flux. Importantly, the selective Li⁺ transport performance was maintained in real salt lake brines. This structural–chemical co-regulation strategy provides a versatile approach for optimizing ion transport membranes in complex separation applications. Full article

The industrial application of modified ion-exchange membranes is limited by complex, discontinuous ex-situ processes. This study introduces an in-situ electro-assembly strategy that enables the direct fabrication of a selective layer within an electrodialysis stack without disassembly. By utilizing a programmed current reversal to orchestrate the sequential deposition of polyethyleneimine (PEI), glutaraldehyde cross-linking, and polystyrene sulfonate (PSS) adsorption, we achieve meticulous interfacial engineering on a commercial cation exchange membrane. Comprehensive characterization confirms the successful construction of a hydrophilic, charge-tuned multilayer, which enhances ion transport kinetics and raises the limiting current density. This method culminates in a membrane with an exceptional Li⁺/Mg²⁺ selectivity of 107.9 and robust stability, retaining a significant selectivity of 47 over 10 cycles in real salt lake brine. This synergistic integration of operational simplicity, interfacial precision, and superior performance establishes a transformative and scalable platform for manufacturing high-performance membranes for selective ion separation from complex brine sources. Full article

Thick (900–1500 µm), crack-free lithium manganese oxide (LMO) electrodes with a polyvinylidene fluoride (PVDF)-based polymer electrolyte were prepared using an innovated slurry casting method. The selectivity and intercalation capacity of the thick electrodes of 900–1500 μm were evaluated in aqueous chloride solutions containing main cations in synthetic Salar de Atacama brine using cyclic voltammetry (CV) measurements. The CV data indicated that a high Li⁺ selectivity of Li/Na = 152.7 could be achieved under potentiostatic conditions. With the thickest electrode, while the mass specific intercalation capacity was 6.234 mg per gram of LMO, the area specific capacity was increased by 3–11 folds compared to that for conventional thin electrodes to 0.282 mg per square centimeter. In addition, 82% of capacity was retained over 30 intercalation/dis-intercalation cycles. XRD and electrochemical analyses revealed that both Faradaic diffusion-controlled or battery-like intercalation and Faradaic non-diffusion controlled or pseudocapacitive intercalation contributed to the capacity and selectivity. This work demonstrates a practical technology for thick electrode fabrication that promises to result in a significant reduction in manufacturing and operational costs for lithium extraction from brines. Full article

Lithium has emerged as a critical energy metal due to its indispensable role in batteries, aerospace applications, new energy vehicles, and large-scale energy storage systems. The accelerated growth of electric mobility and renewable energy storage has led to a substantial increase in lithium demand, thereby exacerbating the prevailing global supply–demand imbalance. To address this challenge, it is imperative to diversify lithium resources and to advance extraction technologies that are both efficient and sustainable. In comparison with conventional hard-rock deposits, liquid resources such as salt lake brines, oilfield brines, and deep-well brines are gaining attention owing to their broad distribution, abundant reserves, and advantages of reduced land use, lower water consumption, and lower carbon emissions. This work presents a critical review of current lithium recovery strategies from brines, including precipitation, solvent extraction, adsorption, nanofiltration/electrodialysis, and electrochemical methods. Each approach is critically evaluated in terms of Li/Mg selectivity, extraction efficiency, operational stability, and environmental compatibility. Precipitation processes offer simplicity but suffer from low Li recovery and high chemical consumption; solvent extraction achieves high selectivity but faces phase and reagent loss; adsorption using Mn-based sieves yields high capacity with good regeneration stability, whereas membrane and electrochemical systems enable continuous lithium recovery with reduced energy input. Distinct advantages and existing gaps are systematically summarized to provide quantitative insights into performance trade-offs among these pathways. Key findings highlight that organophosphorus–FeCl₃ systems and Mn-based lithium-ion sieves show the best trade-off between selectivity and regeneration stability, whereas emerging membrane–electrochemical hybrids demonstrate promise for low-energy, continuous lithium recovery. The prospects for future development highlight highly selective functional materials, integrated multi-technology processes, and greener, low-energy extraction pathways. Full article

In this work, a quantitative analysis of Li in natural brines was carried out by laser-induced breakdown spectroscopy (LIBS) assisted by the τ–algorithm for detailed analysis of the experimental line shapes (τLIBS). Brine samples were collected from different salars located in the Puna plateau (Northwest Argentina) and analyzed by LIBS in the form of solid pressed pellets. The emission intensities of Li I, H_α, and Mg I–II lines were measured and spatially integrated along the line of sight with temporal resolution by using a high-spectral-resolution spectrometer equipped with an intensified charge-coupled device (iCCD) detector. The plasma was characterized through the determination of the electron density and the temperature. The τ–algorithm calculated the optical thicknesses of the Li I lines to generate synthetic intensity profiles that were subsequently fitted to the experimental spectra. By applying the developed τLIBS approach, valuable spectroscopic insight was recovered about the physical processes occurring in the plasma, such as self-absorption. The analytical process involved an univariate external calibration process using the resonant Li I line at 6707.7 Å measured from a series of Li standard samples. Self-absorption effects were evaluated and subsequently compensated. The final LIBS results, with an enhanced accuracy of 15%, were validated by crosschecking them against those obtained with the standard AAS method. Full article

The extraction of lithium and potassium from salt lakes has led to the generation of substantial amounts of magnesium-rich waste streams. These by-products, with their high magnesium content, have contributed to severe environmental degradation in salt lake regions. Therefore, recovering and utilizing magnesium from salt lake resources is a crucial challenge for achieving sustainable development. In this study, magnesium and lithium were separated from evaporated brine—obtained via solar pond technology—using membrane electrolysis. Magnesium was converted into Mg(OH)₂ as a flame retardant, while lithium was refined into battery-grade Li₂CO₃. The final products exhibited high purity, exceeding 99.5% for Mg(OH)₂ and 99.99% for Li₂CO₃. This work systematically investigated the influence of electrolysis temperature on the physicochemical properties of Mg(OH)₂ extracted via membrane electrolysis. The variation in electrolyte temperature was also analyzed in relation to other process parameters, such as electrolyte concentration, current density, and processing time. Results demonstrated that the electrolysis process could maintain a favorable operating temperature through self-heating, even under ambient conditions. Using this electrolysis approach for magnesium–lithium separation from brine, extraction rates of 95.86% for magnesium and 67.46% for lithium were achieved. Full article

Seawater reverse osmosis (SWRO) desalination generates a concentrated brine byproduct rich in dissolved salts and minerals. This study presents an extensive economic and technical analysis of recovering all major ions from SWRO brine, which includes Na, Cl, Mg, Ca, SO₄, K, Br, B, Li, Rb, and Sr in comparison to conventional mining and chemical production of these commodities. Data from recent literature and case studies are compiled to quantify the composition of a typical SWRO brine and the potential yield of valuable products. A life-cycle cost framework is applied, incorporating capital expenditure (CAPEX), operational expenditure (OPEX), and total water cost (TWC) impacts. A representative simulation for a large 100,000 m³/day SWRO plant shows that integrated “brine mining” systems could recover on the order of 3.8 million tons of salts per year. At optimistic recovery efficiencies, the gross annual revenue from products (NaCl, Mg(OH)₂/MgO, CaCO₃, KCl, Br₂, Li₂CO₃, etc.) can reach a few hundred million USD. This revenue is comparable to or exceeds the added costs of recovery processes under favorable conditions, potentially offsetting desalination costs by USD 0.5/m³ or more. We compare these projections with the economics of obtaining the same materials through conventional mining and chemical processes worldwide. Major findings indicate that recovery of abundant low-value salts (especially NaCl) can supply bulk revenue to cover processing costs, while extraction of scarce high-value elements (Li, Rb, Sr, etc.) can provide significant additional profit if efficient separation is achieved. The energy requirements and unit costs for brine recovery are analyzed against those of terrestrial or conventional mining; in many cases, brine-derived production is competitive due to avoided raw material extraction and potential use of waste or renewable energy. CAPEX for adding mineral recovery to a desalination plant is significant but can be justified by revenue and by strategic benefits such as reduced brine disposal. Our analysis, drawing on global data and case studies (e.g., projects in Europe and the Middle East), suggests that metals and salts recovery from SWRO brine is technically feasible and, at sufficient scale, economically viable in many regions. We provide detailed comparisons of cost, yield, and market value for each target element, along with empirical models and formulas for profitability. The results offer a roadmap for integrating brine mining into desalination operations and highlight key factors such as commodity prices, scale economies, energy integration, and policy incentives that influence the competitiveness of brine recovery against traditional mining. Full article

Shale gas wastewater from hydraulic fracturing poses significant environmental risks due to its high salinity and complex inorganic composition. This study investigates the behavior of major and trace inorganic constituents across a full-scale treatment train in the Sichuan Basin, China. Despite multi-stage processes including equalization, flocculation, flotation, biological reactors, membrane filtration, and clarification, key inorganic species such as Cl, Na, Br, Sr, Li, and B remained largely persistent in the final effluent with values of 13,760, 8811, 70, 95.9, 26.6, and 60.2 mg/L, respectively. Geochemical tracers including Br/Cl (average: 0.0022 mM/mM), Na/Br (average: 125 mg/mg), and Sr/Ca (average: 0.15 mM/mM) ratios, combined with halide endmember mixing models, revealed that salinity primarily originated from highly evaporated formation brines, with limited evidence for halite dissolution or external contamination. Elevated Sr (average: 89.3 mg/L) and Ca (average: 274 mg/L) levels relative to Mg (average: 32 mg/L) suggest significant water–rock interaction. Environmental risk assessments showed that concentrations of several elements in treated effluent greatly exceeded national and international discharge or reuse standards. These findings underscore the limitations of conventional treatment technologies and highlight the urgent need for advanced processes and regulatory frameworks that address the unique challenges of high-TDS (total dissolved solids) unconventional wastewater. Full article

Brine with a high magnesium-to-lithium ratio was separated by electrodialysis equipped with a monovalent cation exchange membrane under differing operational parameters. The ionic concentration variations, separation coefficients, lithium recovery ratio, permselectivity coefficient, and Li⁺ flux were analyzed to evaluate the effect of the initial Li⁺/Mg²⁺ mass concentration ratio, applied voltage, and initial volume ratio between the dilute and concentrated compartments on the separation performance of magnesium and lithium. The results showed that the increase in initial Li⁺/Mg²⁺ concentration ratio significantly increased the separation coefficient, lithium recovery ratio, and Li⁺ flux, demonstrating an improvement in the separation performance since the Li⁺ migration was accelerated when less Mg²⁺ competed with Li⁺. As the applied voltage increased from 10 V to 15 V, the separation coefficient increased, and the lithium recovery ratio and Li⁺ flux increased within 60 min; however, as the applied voltage increased to 20 V, the separation coefficient, the lithium recovery ratio, and the Li⁺ flux did not increase, which indicated that an increase in the applied voltage within the limits would contribute to the separation performance. The increase in the initial volume ratio between the dilute and concentrated compartments decreased the separation coefficient and lithium recovery ratio, indicating that the separation performance had declined. Full article

This study investigated the distribution and source of heavy metals and dispersed elements in the high-salinity brine of Qarhan Salt Lake. The brine with an average total dissolved solid content of 332.22 g/L, dominated by Cl⁻ (216.41 g/L) and Mg²⁺ (44.76 g/L), indicated strong evaporation and dolomite dissolution. As (6.57 ± 3.59 μg/L) and Hg (0.48 ± 0.14 μg/L) showed uniform distribution while Li (69.66 mg/L), B₂O₃ (317.80 mg/L), and Zn (5.69 mg/L) were highly enriched, highlighting the resource potential and geochemical complexity. Correlation analysis revealed that water–rock interaction played a key role in element differentiation, with Sr and Ca²⁺/Cl⁻ showing strong positive correlations (r = 0.693/0.768), reflecting isomorphic substitution and dissolution. Meanwhile, Na⁺ and Mg²⁺/Ca²⁺ showed negative correlations (r = −0.732/−0.889), suggesting cation exchange and gypsum precipitation. The self-organizing map yielded four clusters of elements and positive matrix factorization model identified four sources; the elements in the Salt Lake brine mainly came from the river water supply, weathering and leaching of minerals, and dissolution of salt-bearing layers and were locally influenced by human activities. The research provided valuable insights for future sustainable development and the environmental protection of the region. Full article

Lithium and its compounds have become crucial energy metals and industrial necessities. Driven by technological advancements and expanding applications in energy storage and portable electronics, ensuring sustainable lithium supply chains is highly important. Thus, the development of efficient extraction methods from salt-lake brines, particularly those with high Mg²⁺/Li⁺ ratios, has become a priority. Nanofiltration (NF) separation technology has recently emerged as a key process for selective lithium recovery, presenting remarkable advantages over conventional methods. This review systematically assesses the relationships between the polymeric structure and sieving performance of NF membranes for lithium extraction. This research emphasizes the influence of the membrane architecture on ionic selectivity and permeability. Advanced modification strategies for positively charged NF membranes are meticulously analyzed. These strategies include surface functionalization, copolymer design, and hybrid nanocomposite engineering, all of which are aimed at increasing the Mg²⁺/Li⁺ separation efficiency. Moreover, the review delves into innovative membrane module configurations and coupling processes (such as the integration of NF-electrodialysis) to satisfy the requirements of industrial scalability. Finally, the critical challenges and future research directions are highlighted. Our focus lies on cost-effective membrane fabrication, the optimization of long-term stability, and system-level process intensification. This comprehensive analysis not only provides an in-depth mechanistic understanding of high-selectivity lithium extraction from complex brines but also stimulates the rational design of next-generation membranes with precisely tailored ion-transport properties. Full article

With the depletion of solid lithium ore, extracting lithium from salt lake brine has become a critical focus for future endeavors. A four-step method was used to synthesize high-purity H_1.6Mn_1.6O₄ for extracting Li⁺. Porous cubic Mn₂O₃ was hydrothermally synthesized with carbon spheres and surfactants as templates. Then, it was converted to LiMnO₂ by calcining with Li₂CO₃. After roasting and acid pickling, H_1.6Mn_1.6O₄ was successfully synthesized. The impacts of calcination temperature, Li/Mn molar ratio and glucose addition on LiMnO₂ composition, loss percentage of dissolved Mn in precursor, and the adsorption characteristics of the lithium ion sieve were studied. Glucose inhibited the formation of LiMn₂O₄ and promoted the formation of pure LiMnO₂. The resulting precursor without impurities showed porous structure. After acid pickling, H_1.6Mn_1.6O₄ showed a high-adsorption performance and excellent cycle performance. After five cycles, adsorption capacity remained above 30 mg/g, and the loss percentage of dissolved Mn stabilized at about 1%. The Li⁺–H⁺ exchange conformed to pseudo-second-order adsorption dynamics and the Langmuir adsorption isotherm equation, indicating that the adsorption process can be classified as monolayer chemical adsorption. Full article

The rapid expansion of lithium-ion battery (LIB) markets for electric vehicles and renewable energy storage has exponentially increased lithium demand, driving research into sustainable extraction methods. Traditional lithium recovery from brine using evaporation ponds is resource intensive, consuming vast amounts of water and causing severe environmental issues. In response, Direct Lithium Extraction (DLE) technologies have emerged as more efficient, eco-friendly alternatives. This review explores two promising electrochemical DLE methods: Electrodialysis (ED) and Capacitive Deionization (CDI). ED employs ion-exchange membranes (IEMs), such as cation exchange membranes, to selectively transport lithium ions from sources like brine and seawater and achieves high recovery rates. IEMs utilize chemical and structural properties to enhance the selectivity of Li⁺ over competing ions like Mg²⁺ and Na⁺. However, ED faces challenges such as high energy consumption, membrane fouling, and reduced efficiency in ion-rich solutions. CDI uses electrostatic forces to adsorb lithium ions onto electrodes, offering low energy consumption and adaptability to varying lithium concentrations. Advanced variants, such as Membrane Capacitive Deionization (MCDI) and Flow Capacitive Deionization (FCDI), enhance ion selectivity and enable continuous operation. MCDI incorporates IEMs to reduce co-ion interference effects, while FCDI utilizes liquid electrodes to enhance scalability and operational flexibility. Advancements in electrode materials remain crucial to enhance selectivity and efficiency. Validating these methods at the pilot scale is crucial for assessing performance, scalability, and economic feasibility under real-world conditions. Future research should focus on reducing operational costs, developing more durable and selective electrodes, and creating integrated systems to enhance overall efficiency. By addressing these challenges, DLE technologies can provide sustainable solutions for lithium resource management, minimize environmental impact, and support a low-carbon future. Full article

This study investigates Mg isotopes (δ²⁶Mg) in vent fluids from Milos, Aegean Sea, to evaluate phase separation and secondary mineral formation. The δ²⁶Mg vary significantly in Milos, exceeding 0.66‰, allowing for the classification of the fluids into three sub-groups based on chemical characteristics: seawater-like, cave fluids, and submarine-brines. The seawater-like fluids exhibit large δ²⁶Mg variation, −0.64 to −1.18‰, and mostly follow a Rayleigh fractionation trend, with a fractionation factor α = 1.00020 ± 0.00011. The cave fluids are highly acidic, have low Cl, are vapor-rich, and display heavy δ²⁶Mg compositions (−0.52 to −0.63‰). The submarine-brines are characterized by high Cl, high non-volatile metals, and light δ²⁶Mg (−0.65 to −1.00‰). The latter two fluid types represent vapors and brines, respectively, which underwent phase separation at depth in Milos. These δ²⁶Mg values were combined with major/trace elements, as well as Li and B isotopes, to explore possible controlling mechanisms. We report for the first time a shallow submarine hydrothermal system that has a vapor component enriched in heavy δ²⁶Mg, but with no detectable isotopic changes in the brines. It is evident that δ²⁶Mg in vent fluids is unique for separating effects of water/rock interaction and secondary mineral and phase separation at shallow-water systems. Full article

Direct lithium extraction from unconventional resources requires the development of effective adsorbents. Crown ether-containing materials have been reported as promising structures in terms of lithium selectivity, but data on adsorption in real, highly saline brines are scarce. Crown ether-grafted graphene oxides were synthesized using 2-hydroxymethyl-12-crown-4, hydroxy-dibenzo-14-crown-4 and epichlorohydrin as a source of anchoring groups. The obtained carbonaceous materials were used to prepare chitosan–polyvinyl alcohol composites. The prepared materials (and intermediate products) were characterized using FTIR, XRD, Raman spectroscopy and SEM-EDS methods. Adsorption tests were performed in a pure diluted LiCl solution ([Li] = 200 mg/kg) as well as in a real, highly saline oilfield brine ([Li] ≈ 220 mg/kg), and the distribution coefficients (K_d) were determined. The obtained results show that K_d in pure LiCl solution was in the range of 0.9–75.6, while in brine it was in the range of 0.2–2.3. The study indicates that the high affinity for lithium in pure LiCl solution is mostly associated with the non-selective interaction of lithium ions with the graphene oxide matrix (COOH groups). It was also shown that the application of dibenzo-14-crown-4 moiety to graphene oxide modification groups increases the affinity of the composite material for lithium ions compared to an analogous material containing 12-crown-4-ether groups. Full article