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Here, research now demonstrates that solution-processable polymer membranes with hydrophilic subnanometre pores can selectively extract lithium ions from salt-lake brines, offering a potentially sustainable approach to meet the growing demand for lithium in energy storage applications.
Direct lithium extraction (DLE) of brines after geothermal power production offers opportunities to produce environmentally benign “green” lithium; however, some environmental impact is inevitable. We examined solid waste production at geothermal power plants in southern California that are also locations for planned DLE facilities. Currently, the geothermal plants in this region produce approximately 79,800 metric tons (wet weight) per year of solid waste, which represents about 28 metric tons per GWh of net electricity production or approximately 500 mg solids per kg geothermal brine. Approximately 15% of this waste requires management as hazardous waste. Solids produced during power production represent about 0.2% of the total dissolved solids in the brine. Lithium production will require the removal of silica, iron, and other metals as part of the DLE process. Using a mass balance approach, we calculate that precipitation of silica and metals could produce up to an additional 6800 mg solids per kg brine. Calcium occurs at very high concentrations, and the amount of solids disposed in landfills will be dependent on the amount of calcium removed during lithium recovery. Our analysis shows that evaluation of brine chemistry in the context of the DLE process is useful for evaluating the potential solid waste impacts of producing lithium from brines.
A lithium extraction composite comprising: (i) a porous support and (ii) particles of a lithium-selective sorbent material coated on at least one surface of the support, wherein the support has a planar membrane, fiber (or rod), or tubular shape. A method for extracting and recovering a lithium salt from an aqueous solution by use of the above-described composition is also described, the method comprising (a) flowing the aqueous source solution through a first zone or over a first surface of the lithium extraction composite to result in selective lithium intercalation in the lithium-selective sorbent material in the first zone or first surface; and (b) simultaneously recovering lithium salt extracted in step (a) from said lithium-selective sorbent material by flowing an aqueous stripping solution through a second zone or over a second surface of the lithium extraction composite in which lithium ions from the first zone or first surface diffuse.
Lithium (Li), a leading cathode material in rechargeable Li-ion batteries, is vital to modern energy storage technology, establishing it as one of the most impactful and strategical elements. Given the surge in the electric car market, it is crucial to improve lithium recovery from its rich mineral deposits using the most effective extraction technique. In recent years, both industry and academia have shown significant interest in Li recovery from various Li-bearing minerals. Of these, only extraction from spodumene has established a reliable industrial production of Li salts. The current approaches for cracking of the naturally occurring, stable α-spodumene structure into a more open structure—β-spodumene—involve the so-called decrepitation process that takes place at extreme temperatures of ~1100 °C. This conversion is necessary, as β-spodumene is more susceptible to chemical attacks facilitating Li extraction. In the last several decades, many techniques have been demonstrated and patented to process hard-rock mineral spodumene. The objective of this review is to present a thorough analysis of significant findings and the enhancement of process flowsheets over time that can be useful for both research endeavors and industrial process improvements. The review focuses on the following techniques: acid methods, alkali methods, carbonate roasting/autoclaving methods, sulfuric acid roasting/autoclaving methods, chlorinating methods, and mechanochemical activation. Recently, microwaves (MWs), as an energy source, have been employed to transform α-spodumene into β-spodumene. Considering its energy-efficient and short-duration aspects, the review discusses the interaction mechanism of MWs with solids, MW-assisted decrepitation, and Li extraction efficiencies. Finally, the merits and/or disadvantages, challenges, and prospects of the processes are summarized.
This report describes the scale-up and pilot validation of Alpha-En's Reductive Lithium Extraction (RLE) process, which directly converts lithium ions from aqueous brine-derived feedstocks into thin-film lithium metal anodes, demonstrating greater than 50% extraction efficiency, battery performance matching or exceeding commercial lithium metal controls in coin and pouch cells, and continuous roll-to-roll production of a meter-scale lithium metal anode strip.
The rapid growth of lithium-ion battery (LIB) deployment presents critical challenges in sustainable end-of-life management and raw material recovery. Conventional pyrometallurgical and hydrometallurgical methods suffer from high energy demand, lithium loss, and complex wastewater treatment. This study established a universal, highly efficient, and sustainable hydrothermal route for lithium extraction and material recovery from various spent lithium-ion battery cathodes using 1,2,4,5-benzenetetracarboxylic acid (BTCA). The optimized process achieved over 99% lithium leaching efficiency for lithium iron phosphate (LFP) and LiNi x Mn y Co 1–x–y O 2 (NMC), with transition metal coleaching below 1%. It was also broadly applicable to lithium manganese oxide, lithium cobalt oxide, and black mass, achieving 98.5%, 98.95%, and 94.06% leaching efficiencies, respectively. The extracted lithium was directly converted into battery-grade lithium sources, while transition metals were recovered as oxides. Unreacted BTCA was efficiently regenerated and reused without degradation. Electrochemical evaluation confirmed that cathode materials synthesized with recovered lithium exhibit comparable performance to commercial products. Compared to conventional hydrometallurgy, the BTCA-based process increased revenue by over 40% and reduced greenhouse gas emissions by up to 39%. This closed-loop, chemistry-agnostic strategy offered a scalable and economically viable solution for industrial LIB recycling, enabling resource circularity and reducing dependency on primary critical materials.
Efficient lithium recovery from geothermal brines is crucial for the battery industry. Current electrochemical separation methods struggle with the simultaneous presence of Na + , K + , Mg 2+ , and Ca 2+ because these cations are similar to Li + , making it challenging to separate effectively. We address these challenges with a three-chamber reactor featuring a polymer porous solid electrolyte in the middle layer. This design improves the transference number of Li + (t Li+ ) by 2.1 times compared to the two-chamber reactor and also reduces the chlorine evolution reaction, a common side reaction in electrochemical lithium extraction, to only 6.4% in Faradaic Efficiency. Employing a lithium-ion conductive glass ceramic (LICGC) membrane, the reactor achieved high t Li+ of 97.5% in LiOH production from simulated brine, while the concentrations of Na + K + , Mg 2+ , and Ca 2+ are below the detection limit. Electrochemical experiments and surface analysis elucidated the cation transport mechanism, highlighting the impact of Na + on Li + migration at the LICGC interface.
The United States has a large, domestic source of lithium in geothermal fluids, especially at the Salton Sea region of southern California, where estimates of lithium pass-through at geothermal plants exceed 24,000 metric tons per year, based on 2019 geothermal plant operations. Lithium extraction from geothermal brines offers the potential to provide the United States with a secure, domestic supply of lithium to meet the increasing demands of electric vehicles, grid energy storage, portable electronics, and other end-use applications. Additionally, the use of direct extraction technologies allows for a more sustainable lithium supply relative to current evaporative brine and hardrock mining operations in terms of land use, water use, time to market with lithium products, and carbon intensity of operations. This report is part of an effort to assess geothermal brines as a source of commercial lithium supply for the United States. In this study, the National Renewable Energy Laboratory (NREL) reviews and summarizes public technoeconomic analyses of lithium extraction technologies. The work was coordinated with the Critical Minerals Institute at the Colorado School of Mines who focused on supply chain analysis of lithium.
A reliable supply of lithium is required to meet the increased demand for batteries over the coming decades. In this work, we demonstrated the potential to effectively extract lithium from brines by coupling solar-powered evaporation, adsorption, and membrane technologies together. We first synthesized a three-dimensional adsorptive evaporator by coating a lithium manganese oxide material onto a cotton stick using an easily scalable, one-step method. An osmotic membrane was then installed at the root of the evaporator to enhance the lithium to magnesium selectivity, prevent scaling caused by divalent cations, and thus further increase the water evaporation flux. The operation of the dual membrane-adsorption evaporator is entirely driven by osmosis and capillary force, demanding no extra energy input. The integration of the osmotic membrane was found to increase the lithium to magnesium selectivity over 10-fold to higher than 40. The dual process also produced high lithium to calcium selectivity and proved to sustain long-term stability by self-managing its internal osmotic pressure. Last, a test was done in three simulated brine solutions with varied brine chemistry and the evaporation rate stayed high and consistent throughout the long-term test. This illustrates that this technology can be used in varied brine solutions throughout the world providing efficient lithium capture and separation from competing divalent cations.
Aluminum hydroxide, an abundant mineral found in nature, exists in four polymorphs: gibbsite, bayerite, nordstrandite, and doyleite. Among these polymorphs gibbsite, bayerite, and commercially synthesized amorphous aluminum hydroxide have been investigated as sorbent materials for lithium extraction from sulfate solutions. The amorphous form of Al(OH) 3 exhibits a reactivity higher than that of the naturally occurring crystalline polymorphs in terms of extracting Li + ions. This study employed high-temperature oxide melt solution calorimetry to explore the energetics of the sorbent polymorphs. The enthalpic stability order was measured to be gibbsite > bayerite > amorphous Al(OH) 3 . The least stable form, amorphous Al(OH) 3 , undergoes a spontaneous reaction with lithium, resulting in the formation of a stable layered double hydroxide phase. Consequently, amorphous Al(OH) 3 shows promise as a sorbent material for selectively extracting lithium from clay mineral leachate solutions. Further, this research demonstrates the selective direct extraction of Li + ions using amorphous aluminum hydroxide through a liquid–solid lithiation reaction, followed by acid-free delithiation and relithiation processes, achieving an extraction efficiency of 86%, and the maximum capacity was 37.86 mg·g –1 in a single step during lithiation. With high selectivity during lithiation and nearly complete recoverability of the sorbent material during delithiation, this method presents a circular economy model. Furthermore, a life cycle analysis was conducted to illustrate the environmental advantages of replacing the conventional soda ash-based precipitation process with this method, along with a simple operational cost analysis to evaluate reagent and fuel expenses.
Membrane-based technologies are essential for realizing sustainable ion-sieving processes such as lithium extraction. Much effort was devoted to designing new membrane materials, whereas the effect of charge distribution has been largely overlooked. Here, we filled this knowledge gap by providing a quantitative transport model for selective ion diffusion through a charge mosaic membrane (CMM). Composed of alternating regions of Li-selective ceramic and anion-selective polymeric materials, CMMs offered the unique advantage of promoting the transport of both Li + and anions while blocking other cations. As a result, the membrane achieved a high Li/Mg selectivity of 62 and a high permeation rate of 59 mmol·m −2 ·h −1 at a low feeding concentration of 30 mM, without any external driving force. Systematical experiments revealed the influence of brine Mg/Li ratio and membrane ceramic/polymer ratio on the overall extraction rate, which was consistent with the prediction of our transport model. In conclusion, the model developed in this work not only presented the design strategies of CMMs for Li extraction but also provided guidance for the development of other ion-sieving processes in general.
The demand for lithium, a key component in rechargeable batteries for electric vehicles and renewable energy storage systems, has surged in recent years. Meeting this demand requires efficient extraction methods that are both environmentally friendly and economically viable. This study investigates the utilization of the high-capacity sorbent amorphous aluminum hydroxide for enabling efficient direct lithium extraction at low temperatures. Traditional extraction methods often involve acid-leaching and energy-intensive processes that are not only expensive but also environmentally taxing. In contrast, our approach leverages the exceptional sorption properties of amorphous aluminum hydroxide to facilitate lithium extraction directly from brine, achieving extraction efficiencies of 94.4% in case 1 and 96.2% in case 2 at low temperatures. Kinetic modeling using the Avrami–Erofe’ev framework reveals a nucleation-growth mechanism ( n = 0.71, k = 0.131 h –1 ), providing quantitative insights into the solid-state phase transformation process. This method significantly reduces energy consumption and minimizes the environmental footprint. Through systematic experimentation and optimization, we demonstrate the effectiveness and scalability of our approach, highlighting its potential to revolutionize lithium extraction processes. Our findings highlight the potential of high-capacity sorbents, particularly amorphous aluminum hydroxide toward sustainable lithium production, contributing to the advancement of clean-energy technologies.
In this presentation, the speaker discusses the research that has been carried out at NETL regarding direct lithium extraction. The three main discussing points are as follows: developing high-capacity lithium-ion sieve sorbent using mineral streams associated with critical minerals; demonstrating the sorbent ability to recover lithium from oil/gas produced waters and geothermal brines; and assessing the feasibility of large-scale implementation through technoeconomic analysis.
With the burgeoning reliance on lithium-ion batteries for sustainable energy solutions and electric transportation, the environmental and resource management associated with battery disposal are increasingly critical. Addressing these challenges necessitates innovative recycling techniques that recover valuable battery components, particularly lithium. This research introduces a universal, eco-friendly approach tailored for the efficient selective extraction of lithium from both single and mixed cathode materials, achieving impressive selective leaching efficiencies of lithium (99.51 % for LFP, 90 % for NMC, and 97.24 % for mixed cathode). Surprisingly, leaching efficiency of lithium from NMC can be significantly improved by introducing LFP since LFP can remove the dense transition-metal salts on the surface of NMC. The extracted lithium is recovered as lithium carbonate with battery-grade purity. This study also highlights the reuse of formic acid and the adoption of oxygen as an oxidizing agent to prevent wastewater production. Therefore, this method provides a robust foundation for sustainable lithium battery recycling.
Spinel-structured ordered-LiNi 0.5 Mn 1.5 O 4 (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from lithium-ion battery. O-LNMO undergoes two two-phase reaction at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of solid solution reaction exists for charge and discharge at both slow and fast rate. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from asynchronized reaction among the particles. Finally, during fast discharge, it is likely a core-shell mechanism involving transition from Li 0+x Ni 0.5 Mn 1.5 O 4 to Li 1+x Ni 0.5 Mn 1.5 O 4 in the outer layer of particles. The Li 0.5 Ni 0.5 Mn 1.5 O 4 phase is suppressed during fast discharge and only appears through Li redistribution upon relaxation.
Electrochemical technologies add a unique dimension for ore refinement, representing tunable methods that can integrate with renewable energy sources and existing downstream process flows. However, the development of electrochemical extraction technologies has been impeded by the technological maturity of hydro- and pyro-metallurgy, as well as the electrical insulating properties of many metal oxide ores. The fabrication and use of carbon/insulating material composite electrodes has been a longstanding method to enable electrochemical activation. Here, using real hectorite ore, we employ this technical approach to fabricate hectorite-carbon black composite electrodes (HCCEs) and achieve electrochemical activation of hectorite. Anodic polarization results in lithium-ion release through a multi-step chemical and electrochemical mechanism that results in 50.7 ± 4.4% removal of lithium from HCCE, alongside other alkaline ions. This technical proof-of-concept study underscores that electrochemical activation of ores can facilitate lattice deterioration and ion removal from ores.
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