No full-text available
To read the full-text of this research,
you can request a copy directly from the authors.
Lithium extraction from Chinese salt-lake brines: Opportunities, challenges, and future outlook
Abstract
Chinese salt-lake brine is mainly of the magnesium sulfate subtype with a high Mg/Li ratio. Mining lithium from Chinese salt-lake brine has been a decades-long technical challenge. The pros and cons of various technologies are briefly discussed. Chemical extraction has been the most important technology for the recovery of lithium from Chinese salt-lake brine with a high Mg/Li ratio. Several other innovative technologies, including lithium ion sieves, membrane separation, and electro–electrodialysis, have also emerged as potential options.
... Currently, the recovery of lithium resources involves various methods, such as extraction, precipitation, and adsorption. Extraction methods separate lithium by adding organic solvents and other extractants (Song et al. 2017;Bruce et al. 2011). For example, the use of the benzoyltrifluoroacetonetrioctylphosphine oxide-kerosene as an extractant has a high extraction rate for lithium and can effectively enrich lithium in brine (Bruce et al. 2011). ...
... For example, the use of the benzoyltrifluoroacetonetrioctylphosphine oxide-kerosene as an extractant has a high extraction rate for lithium and can effectively enrich lithium in brine (Bruce et al. 2011). The tributyl phosphate-kerosene-ferric chloride system can also obtain high separation factors under complex solution environments (Song et al. 2017). However, extraction methods often require solution pretreatment and the addition of several agents to change the solution environment, such as pH, to improve extraction efficiencies (Shi et al. 2019). ...
With the continuous development of global industry and the increasing demand for lithium resources, recycling valuable lithium from industrial solid waste is necessary for sustainable development and environmental friendliness. Herein, we employed ion imprinting and capacitive deionization to prepare a new electrode material for lithium-ion selective recovery. The material morphology and structure were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and other characterization methods, and the adsorption mechanism and water clusters were correlated using the density functional theory. The electrode material exhibited a maximum adsorption capacity of 36.94 mg/g at a Li⁺ concentration of 600 mg/L. The selective separation factors for Na⁺, K⁺, Mg²⁺, and Al³⁺ in complex solution environments were 2.07, 9.82, 1.80, and 8.45, respectively. After undergoing five regeneration cycles, the material retained 91.81% of the initial Li⁺ adsorption capacity. Meanwhile, the electrochemical adsorption capacity for Li⁺ was more than twice the corresponding conventional physical adsorption capacity because electrochemical adsorption provides the energy needed for deprotonation, enabling exposure of the cavities of the crown ether molecules to enrich the active sites. The proposed environment-friendly separation approach offers excellent selectivity for Li⁺ recovery and addresses the growing demand for Li⁺ resources.
... Because of its importance, reliability, and low cost, this mineral is the best bet for meeting the rising demand for lithium [9]. Lithium is also found in continental brines in the Salars of South America and the Qinghai Tibet Plateau in China, which together make up the second largest source of lithium in the world [10]. Differentiating methods might lead to different total resource levels reported by different authorities. ...
... The extraction agent, the co-extraction agent, and the diluent are the three components that make up the solvent system. This technique allows for the dissolution of lithium chloride while preserving selectivity against ions that are not desirable [10]. Tributyl phosphate (TBP) is a powerful extractant that may be used to selectively recover lithium from magnesium-rich brines. ...
The global demand for lithium, which is indispensable for electric cars and electrical devices, has increased. Lithium recovery from oilfield-produced water is necessary to meet the growing need for lithium-ion batteries, protect the environment, optimize resource utilization, and cut costs to ensure a successful energy transition. It is useful for keeping water supplies in good condition, adhering to legal requirements, and making the most of technological advances. Oil and gas companies might see an increase in revenue gained through the lithium extraction from generated water due to the recouping of energy costs. Therefore, this review focuses on contamination and treatment strategies for the oilfield-produced water. It includes a discussion of the global lithium trade, a financial analysis of lithium extraction, and a comparison of the various methods currently in use for lithium extraction. It was evaluated that economic considerations should be given priority when selecting environmentally friendly methods for lithium recovery from oilfield-produced water, and hybrid methods, such as adsorption–precipitation systems, may show promising results in this regard. Lastly, future prospects for the lithium industry were also discussed.
... 4 ± 7 Other applications of lithium, such as food and pharmaceutical industries, aviation and aerospace sectors, electrical engineering, nuclear power engineering and manufacture of ceramics, glass, lubricants, synthetic rubber, etc., are less abundant, but no less significant. 8 Specialists agree that lithium is one of the critically important chemical elements for the development of the world economy and that efficient lithium production is a priority for the strategic development of many countries. 2,8,9 There are three main sources of lithium: Ð hard rock minerals; Ð highly concentrated natural solutions of lithium salts (mine waters, formation waters, brines, etc.); Ð spent LIBs. ...
... 8 Specialists agree that lithium is one of the critically important chemical elements for the development of the world economy and that efficient lithium production is a priority for the strategic development of many countries. 2,8,9 There are three main sources of lithium: Ð hard rock minerals; Ð highly concentrated natural solutions of lithium salts (mine waters, formation waters, brines, etc.); Ð spent LIBs. ...
В последние годы в связи с резким увеличением спроса на литий возрос интерес исследователей к проблеме его извлечения (получения): согласно базе данным Scopus, за 2021 г. по данной проблеме опубликовано около 3000 научных статей. Усилия многих специалистов направлены на разработку новых, более экономичных и экологичных, мембранных технологий извлечения лития, взамен применяемых реагентных методов. В обзоре представлена актуальная информация о традиционных и перспективных методах извлечения лития из природных растворов и растворов, получаемых при утилизации использованных батарей. Основное внимание уделено мембранным методам. Классифицированы и проанализированы известные подходы, описаны экспериментальные и теоретические аспекты мембранного разделения ионов, обсуждены известные механизмы разделения и их математические модели. Рассмотрены сравнительно хорошо развитые на лабораторном уровне баро- и электромембранные методы, которые ориентированы на выделение ионов лития и других однозарядных катионов из смешанных растворов, содержащих в больших количествах магний и кальций. Проведено сравнение результатов применения коммерческих и лабораторных мембран. Проанализированы новейшие подходы, позволяющие эффективно выделять ионы лития из смеси однозарядных катионов, в том числе перспективные гибридные электробаромембранные методы.
Библиография — 295 ссылок.
... Approximately 80% of the worldwide market is made up of lithium compounds, which include carbonate, hydroxide, and chloride. These compounds are in high demand [13][14]. Large concentrations of lithium in aqueous solutions are a more widely used way of getting lithium because of its accessibility and lower cost of lithium separation. ...
The solubility of components in the system potassium sulfate-lithium sulfate-water was studied using the visual-polythermal method in a wide range of temperatures and concentrations. The phase diagram delineates the crystallization fields of ice, Li 2 SO 4 , Li 2 SO 4 ·H 2 O, K 2 SO 4 , K 2 SO 4 ·H 2 O and the new phase Li 2 SO 4 ·K 2 SO 4. Based on observations of the polythermal solubility diagram, the crystallization regions of ice Li 2 SO 4 , Li 2 SO 4 ·H 2 O, K 2 SO 4 , K 2 SO 4 ·H 2 O and the new phase Li 2 SO 4 ·K 2 SO 4 are delimited. These fields converge at six triple nodal points, where the equilibrium compositions of solutions and the temperature of the corresponding crystallization are determined. The study of the behavior of potassium sulfate-lithium sulfate salts in water is of great importance in determining the solubility, crystallization, and interaction between salts at different ratios, and temperatures and contributes to determining the points of separate extraction of individual salts from solutions. The formation of a new compound was confirmed by IR spectroscopic, chemical and X-ray phase analysis methods.
... The most concentrated are the salt lakes, in which the lithium content reaches up to 1000 ppm. The presence of alkali and alkaline earth elements, especially magnesium, in brines complicates the problem of lithium extraction [13][14]. On the world market, lithium compounds such as carbonate, chloride, and hydroxide are in great demand, accounting for up to 80% of the market [15]. ...
... The simplicity of the traditional extraction procedure, i.e., evaporation and precipitation, and the abundance of brine resources result in reduced operational costs and consistent production capabilities, making saline lake brines more economically viable source of Li. As a consequence of these advantages, saline lake brines have become one of the most desirable sources for Li extraction in the current circumstance of rising Li demand (Liu et al., 2019;Song et al., 2017). The extraction of Li from industrial effluent is another promising option, which offers a number of advantages that reflect the dual goals of resource recovery and environmental sustainability. ...
... Compared to the PA selective layer prepared from traditional IP, the cross-linking degree of the PA selective layer prepared from OSARIP is significantly increased (from 74.7% to 88.6%) based on the elemental composition analysis of X-ray photoelectron spectroscopy (XPS) (Fig. 1c, d, and Supplementary Figs. [3][4][5][6], and the membrane shows less negatively charged due to less residual unreacted groups (see Supplementary Fig. 7). Figure 1d−g displays the topological structure of the PA NF membrane prepared from both traditional IP and OSARIP. In comparison, the PA NF membrane prepared from OSARIP displays small convex spots and a thinner PA selective layer (∼67 nm for the membrane prepared from traditional IP and ∼55 nm for the membrane prepared from OSARIP). ...
Achieving high selectivity of Li⁺ and Mg²⁺ is of paramount importance for effective lithium extraction from brines, and nanofiltration (NF) membrane plays a critical role in this process. The key to achieving high selectivity lies in the on-demand design of NF membrane pores in accordance with the size difference between Li⁺ and Mg²⁺ ions, but this poses a huge challenge for traditional NF membranes and difficult to be realized. In this work, we report the fabrication of polyamide (PA) NF membranes with ultra-high Li⁺/Mg²⁺ selectivity by modifying the interfacial polymerization (IP) process between piperazine (PIP) and trimesoyl chloride (TMC) with an oil-soluble surfactant that forms a monolayer at oil/water interface, referred to as OSARIP. The OSARIP benefits to regulate the membrane pores so that all of them are smaller than Mg²⁺ ions. Under the solely size sieving effect, an exceptional Mg²⁺ rejection rate of over 99.9% is achieved. This results in an exceptionally high Li⁺/Mg²⁺ selectivity, which is one to two orders of magnitude higher than all the currently reported pressure-driven membranes, and even higher than the microporous framework materials, including COFs, MOFs, and POPs. The large enhancement of ion separation performance of NF membranes may innovate the current lithium extraction process and greatly improve the lithium extraction efficiency.
... Lithium concentrations in geothermal waters can range anywhere from 1 to 100 ppm [9,19], whereas lithium processing and manufacturing face obstacles by the presence of several pollutants in geothermal fluids, along with significant levels of other metals [20]. In saline lakes, lithium concentrations range from 100-1000 ppm and due to the high concentration of salts, particularly magnesium, makes the treatment of brines difficult [21]. Thus, the presence of high concentrations of alkaline and alkaline earth elements significantly complicates the process of extracting lithium from natural fluids [22]. ...
An increasing number of electric vehicles, hybrids, and synergistic types are adding electronic components, driving up demand for
lithium and its derivatives. These chemicals comprise 80% of the worldwide market and come in forms such as carbonate, lithium hydroxide
and mineral concentrates. The use of lithium is predicted to surge by 60% in the coming years due to the proliferation of electric vehicles.
This demands efficient and rapid deposit detection methods as well as economical and high-resolution exploration equipment. The
quantity and geographical distribution of fossil and ore mineral deposits can be easily mapped using hyperspectral photography. Since
salt lakes, oceans, and geothermal water hold the majority of the world’s lithium reserves ranging from 70% to 80%, these areas are ideal
for the lithium extraction process. In this regard, there is an increase in research targeted at industrial lithium production from water
resources. Recycling lithium-ion batteries is an alternative method that can be utilized to increase the production of lithium. Geothermal
waters have lower lithium contents than brines and some of the processes are not suitable. Evaporation methods, solvent extraction,
membrane technology, nanofiltration and adsorption can all be used to extract lithium from liquid media. Thus, lithium extraction from
aqueous solutions was the focus of this review article, which aimed to provide straightforward technical solutions, low costs, decreased
environmental impact and excellent selectivity for the lithium industry.
... Thus, the high Mg/Li ratios of the Bam salt plug brines make them unsuitable for conventional evaporation/ extraction techniques. However, many brines such as Uyuni brine do not show a suitable chemical composition to recovering Li by the use of classical techniques 48 , or 78% of the salt-lake brines in Western China have high Mg 2+ /Li + ratios up to 500 54 . In spite of specified characteristics, these deposits are considered as future resources for lithium, although their exploration depends on the development of new methods. ...
Lithium (Li) is a scarce and technologically important element; the demand for which has recently increased due to its extensive consumption, particularly in manufacturing of Li-ion batteries, renewable energy, and electronics. Li is extracted from brines, pegmatite, and clay minerals; though extraction from brines is economically preferred. More than 200 salt plugs are in the Zagros Mountains which represent potential sources for Li exploration. This preliminary study collected first data on the abundance of Li in the salt plugs in southern Iran, and investigated Li distribution during evaporation of halite-producing brine ponds. The XRD analysis of powdered samples showed that gypsum and halite are the dominant solid phases in the ponds in which Li is concentrated in gypsum, while halite is depleted of Li. ICP-MS and ICP-OES analyses showed that Li in brines is concentrated during the evaporation by factors up to 28 with total contents up to 40 mg kg‒1. The Mg/Li ratio was higher than 70, which makes the brine unsuitable for conventional evaporation extraction techniques which require Mg/Li ratios of less than 6. Considering that 25 mg kg‒1 is a suitable concentration of Li for exploration purposes, the results of this study suggest that with the advancement of extraction techniques, the depletion of presently used high-grade Li reserves, the increasing demand for lithium, the need for extraction from diverse sources, and the exploration of new resources, the salt plug brines have an exploratory potential for Li in the future.
... Salt lake brines widely distributed in China with the characteristics of high Mg/Li ratio and degree of mineralization due to coexisting with some competitive cations (i.e. Na + , K + , Ca 2+ and Mg 2+ ) (Song et al., 2017;Sun et al., 2015), which cause the extreme difficulties for high-efficient recovery lithium from salt lake brines (Chen et al., 2017;Liu et al., 2019;Peiro et al., 2013). Geothermal water is rich in Li + (20-50 mg L − 1 ) (Kumar et al., 2019), making it a promising liquid source with potential applications. ...
With the increasing application of the industrialization of lithium and its derivatives, there has been a surge of interest in recovering this resource from liquid sources. However, synthesizing adsorbents with industrial significance is still a significant challenge. Herein, the precursor Li1.6Mn1.6O4 of H1.6Mn1.6O4 powder absorbent with the highest theoretical adsorption capacity and the lowest Mn dissolution loss rate was first synthesized by hydrothermal or high-temperature solid phase method. The commercialized wet spinning apparatus, which has convenient operation and a simple process, was used to prepare PVDF/HMO spinning fiber to recover lithium resources from geothermal water. It has a large specific surface area of 31.45 m2 g−1 and a pore size of 9.04 nm, and the adsorption capacity was 14.95 mg g−1, with the distribution coefficient of Li+ being 1404.96 mL g−1. Furthermore, the equilibrium was reached within just 2 h at pH 12, and the elution time was just 1 h. Even after the fifth cycle, the adsorption capacity remained high at 14.21 mg g−1. These characteristics indicate that the new material has excellent application potential for lithium recovery from geothermal water.
... Primary sources for lithium extraction are obtained from spodumene ores 16 and some salt lakes. 17,18 The increase in mining activity and the extraction of lithium from lithium mines in the last few decades has caused environmental destruction and endangered the health of wildlife and local populations. 19,20 Thus, the detection of lithium in environmental samples is required to control each step of the extraction processes. ...
Application of lithium in portable electronic devices, medical field, catalysts, and so on has been increased in recent years because of unique properties of lithium. Therefore, detection and sensing of...
... At present, the global supply of lithium resources is mainly divided into mineral and brine. Thereinto, the lithium extraction from mineral possesses advantages of highly-efficient production and mature fabrication technology, but this method shows higher cost and heavier pollution compared with the lithium extraction from brine [4]. In addition, brine-based lithium sources are approximately four times as much as mineral-based lithium sources [5]. ...
Lithium is known as the “white petroleum” of the electrification era, and the global demand for lithium grows rapidly with the quick development of new energy industry. The aqueous solutions, such as salt lake brine, underground brine, and seawater, have large lithium reserves, thus this kind of lithium resource has become a research hotspot recently. Compared with other lithium extraction technologies, electro-sorption method shows good prospects for practical applications with advantages in the aspects of efficiency, recovery ratio, cost, and environment. Herein, this review covers recent progress on electro-sorption technology for lithium recovery from aqueous solutions, including the concept illustration, research progress of the applied working electrodes and counter electrodes, and the evaluation indicators of electro-sorption system. Meanwhile, some prospects for the development of this technology are also proposed. We hope this review is beneficial for the construction of high-efficient electrochemical lithium recovery system to achieve an adequate lithium supply in the future.
... У світі існують території, поверхневі води яких містять високі рівні літію. Природні розсоли з високим вмістом літію знаходяться на півночі Чилі (1400-1500 мг/л) 31 , у Китаї (560-1300 мг/л) 32 , Болівії (700-900 мг/л) 33 і Аргентині (520-620 мг/л) 34 .Озера, ропа яких містить нижчі концентрації літію (200 мг/л) розташовані в США 35 . ...
... Seawater is a promising source of various minerals such as sodium, magnesium, potassium, and lithium compounds, and has been mined for thousands of years. 1,2 Compared to traditional land-based mining, seawater mining poses reduced environmental and health risks, making it a viable alternative. 3,4 However, the low salt concentrations in seawater make it an expensive and energy-intensive process, which has hindered its widespread adoption. ...
Bulk evaporation of brine is a sustainable method to obtain minerals with the inherent advantage of selective crystallization based on ion solubility differences, but it has a critical drawback of requiring a prolonged time period. In contrast, solar crystallizers based on interfacial evaporation can reduce the processing time, but their ion-selectivity may be limited due to insufficient re-dissolution and crystallization processes. This study presents the first-ever development of an ion-selective solar crystallizer featuring an asymmetrically corrugated structure (A-SC). The asymmetric mountain structure of A-SC creates V-shaped rivulets that facilitate solution transport, promoting not only evaporation but also the re-dissolution of salt formed on the mountain peaks. When A-SC was employed to evaporate a solution containing a mixture of Na+ and K+ ions, the evaporation rate was 1.51 kg/m2h and the relative concentration of Na+ to K+ in the crystallized salt was 4.45 times higher than that in the initial solution.
NTf2⁻-based ionic liquids (ILs)/tri-n-butyl phosphate (TBP) systems can be used for extraction of Li⁺, but ILs are very expensive and their cations can cause the contamination of the aqueous phase in the extraction process. In this study, an inexpensive raw material lithium bis(trifluoromethanesulphonyl)imide (LiNTf2) is used to prepare extraction organic phase NaNTf2·TBP, which can avoid the contamination of the aqueous phase in the extraction process. The preparation conditions of extraction organic phase NaNTf2·TBP were investigated. The extraction conditions of NaNTf2·TBP system were also studied, and under the optimal extraction condition, the single extraction efficiency of Li⁺ is 91.7%. The extraction system is stable after seven extraction cycles, and it has good prospects for application in extraction of Li⁺ from brine with a high Mg/Li ratio.
Lithium, the lightest alkali metal, has been called the “new white gold” because of its limited availability and critical importance in arising applications in clean energy, like hybrid and electric vehicles. However, the rapidly growing demand for lithium, combined with its low global production rates, has led to concerns regarding the development of new technologies that require this critical mineral. For this reason, there is a need for cost-effective, energy-efficient, and environmentally friendly approaches to isolate lithium from sustainable resources like brine, ores, and seawater. In this context, solvent extraction is a promising technique for lithium recovery from these sources that has advantages over other approaches like precipitation, solid-state adsorption, and membranes. However, there are few processes in industry that use solvent extraction for lithium extraction and purification. The scarce use of this method industrially is possibly a consequence of critical knowledge gaps that need to be addressed prior to the optimization of processes with suitably high lithium selectivity and extraction efficiency. This review bridges these gaps by highlighting the coordination chemistry of lithium and discussing the requirements for developing highly selective lithium chelators for solvent extraction. Additionally, the lithium coordination properties and solvent extraction performance of macrocyclic and acyclic chelator classes, as well as ionic liquid extraction systems, used to extract lithium from artificial solutions, brines, and seawater are reviewed.
The unbalanced supply and demand of lithium (Li) has elevated the urge for its extraction owing to the accelerated surge of battery and electric vehicle (EV) industries to meet the carbon emission reduction target. As the cost of extracting Li from brine is typically 30–50% lower than conventional hard-rock sources, this work intends to critically analyze the evolution of direct lithium extraction (DLE) methods employed in Salt Lake brine with various magnesium/lithium (Mg/Li) mass ratios whereas the lithium brine concentration (LBC) methods seek to concentrate the Li brine and eliminate contaminants without isolating the Li from the brine. Solvent extraction, precipitation, adsorption, membrane technology, and electrochemical extraction are the developed methods for Li extraction from Salt Lake brine. This review focuses on the mechanism, workflow, and comparative analysis of different methods. Moreover, recent technological advancements to handle the high Mg/Li ratio, such as modification of adsorption using ion sieves, liquid-membrane electrodialysis, and efficient multicomponent doping electrode materials, have also been discussed in depth. Although it was previously believed that solvent extraction was only feasible for low Mg/Li ratio brines, it has recently been commercially applied for high Mg/Li ratio brines in China. Precipitation is more ecology-friendly and economically favorable because of its low cost. Li extraction from brines with high Mg/Li ratios also shows promising performance using aluminate (Al) precipitants and novel Mg precipitants. However, during Mg precipitation, there is a significant loss of Li. On the other hand, in the cost-effective adsorption method, aluminium salt adsorbents are industrially used, yet low adsorption capacities limit their application. Recently, ion-exchange methods have gained popularity, as ‘Li sieves’ exhibit remarkable selectivity and adsorption towards Li-ions and are effective at high Mg/Li ratios. Powdered ionic sieves have low fluidity and solution permeability despite their strong affinity and adsorption capacity. Membrane technology is promising because of the benefits of improved energy consumption, simple controls, high separation rates, and the continuity of the process, yet as an emerging technology, its commercial viability is not proven. Nevertheless, a coupled “adsorption-membrane” technique has been developed and used in China for Salt Lake brines with low Li grades. Furthermore, exceptional selectivity, low energy demand, and minimal impact on the environment of electrochemical methods make Li extraction from brine promising. Being a recent technology, there is ample scope for improving electrode materials and understanding the process mechanism and cell configuration. Lastly, perspectives on the future Li extraction from brines are conferred in this article. By combining the methods (i.e., adsorption and ion exchange, membrane technology, and electrochemical process), the growth potential exists for an efficient, cost-effective, green, and sustainable extraction technology for Li from Salt Lake brine with a high Mg/Li ratio.
In this study, a new extraction system NaPF6 + NaClO4 + TBP has nearly the same extraction efficiency of Li⁺ as the NaPF6 + TBP system, and nearly the same stripping efficiency of Li⁺ as NaClO4 + TBP system. The effect of NaClO4 and NaPF6 concentration, and phase ratio on extraction efficiency was investigated. At the optimal conditions, the single extraction efficiency of Li⁺ is 77.1%. The stripping efficiency of Li⁺ reaches 90.7% using pure water as a stripping agent with the volume ratio of the aqueous phase to the organic phase (A/O) of 3. TBP + NaPF6 + NaClO4 system has great potential in Li⁺ extraction from Mg²⁺ rich solution.
To address the increasing demand for lithium, the recovery of lithium from salt lake brines has garnered significant attention. Techniques have been developed; however, these approaches exhibit drawbacks such as high energy consumption, excessive freshwater usage, and substantial dissolution losses, presenting environmental concerns. This review discusses the application and characteristics of four extractant systems used in solvent extraction: organophosphates, ionic liquids, crown ethers, and β-diketones. Furthermore, we present the optimization of organophosphate systems to make them more environmentally friendly. Optimization encompasses four key aspects: synergistic extractants, coextractants, diluents, and main extractants. Solvent extraction is a simple, cost-effective, and environmentally benign technique for lithium extraction from brine. Modifying the structure of these extractants can reduce dissolution rates and improve extraction efficiencies.
Achieving high selectivity of Li ⁺ and Mg ²⁺ is of paramount importance for effective lithium extraction from brines, and nanofiltration (NF) membrane plays a critical role in this process. The key to achieving high selectivity lies in the on-demand design of NF membrane pores in accordance with the size difference between Li ⁺ and Mg ²⁺ ions, but this poses a huge challenge for traditional NF membranes and difficult to be realized. In this work, we report the fabrication of polyamide (PA) NF membranes with ultra-high Li ⁺ /Mg ²⁺ selectivity by modifying the interfacial polymerization (IP) process between piperazine (PIP) and trimesoyl chloride (TMC) with an oil-soluble surfactant that forms a monolayer at oil/water interface, referred to as OSARIP. The OSARIP benefits to regulate the membrane pores so that all of them are smaller than Mg ²⁺ ions. Under the solely size sieving effect, an unprecedentedly high Mg ²⁺ rejection rate of 99.96% and Li ⁺ /Mg ²⁺ selectivity over 4000 are achieved. This value is one to two orders of magnitude higher than all the currently reported pressure-driven membranes, and even higher than the microporous framework materials, including COFs, MOFs, and POPs. The large enhancement of ion separation performance of NF membranes may innovate the current lithium extraction process and greatly improve the lithium extraction efficiency.
The demand for lithium extraction from salt-lake brines is increasing to address the global lithium supply shortage. Nanofiltration membrane-based separation technology with high Mg ²⁺ /Li ⁺ separation efficiency has shown great potential for lithium extraction. However, it usually requires diluting the brine with a large quantity of freshwater in the pre-treatment stage and only yields Li ⁺ -enriched solution. Inspired by the process of selective water/ion uptake and salt secretion in mangroves, we report here the direct extraction of lithium chloride (LiCl) powder from salt-lake brines by utilizing the synergistic effect of ion separation membrane and solar-driven evaporator. The ion separation membrane-based solar evaporator is a sandwich structure consisting of an upper photothermal layer to evaporate water, a hydrophilic macroporous membrane in the middle to generate capillary pressure as the driving force for water transport, and an ultrathin ion separation membrane at the bottom to allow Li ⁺ to pass through and block other multivalent ions. This process exhibits outstanding lithium extraction capability. LiCl powder with a purity of 94.2% can be directly collected on the surface of the evaporator. When treating simulated salt-lake brine with ion concentration as high as 348.4 g L − 1 , the Mg ²⁺ /Li ⁺ ratio is reduced by 66 times (from 19.8 to 0.3). This research combines ion separation with solar-driven evaporation to directly obtain LiCl powder, providing a new and efficient approach for lithium extraction.
Geothermal fluids have the potential as important sources of precious minerals and metals. There are several hydrometallurgical techniques by which geothermal fluid solutions can be processed to extract and purify metals and minerals such as potassium, manganese, zinc, and lithium. The primary methods for extraction of salt and base metals from geothermal water include precipitation, electrodialysis, reverse osmosis, adsorption, electrochemical intercalation, and ion exchange. Among several methods discussed so far membrane and adsorption methods can be one of the suitable methods for extraction of salt and base metals, respectively. The article also summarizes various mathematical modeling used to study dynamic behavior and kinetics of column adsorption. The three most widely used column models, i.e., Thomas, BDST, and Yoon–Nelson are discussed herein, that help to estimate the adsorption capacity and intensity giving an overview of mechanism and forces responsible for column sorption process. The elaborate discussion on mechanistic forces and factors responsible for metal extraction by sorption makes this review significant and preferable. Therefore, the article aims to provide deep insights and a quick overview of salt and base metal sources, their extraction processes, column sorption dynamics, kinetic modeling, and mechanisms in one sight.
Graphical Abstract
Work flow for Base metal Extraction from geothermal water.
Ion sieving is a critical process employed in various applications, such as desalination and ion extraction. Nevertheless, achieving rapid and accurate ion sieving remains an exceptionally difficult task. Drawing inspiration from the effective ion sieving capabilities of biological ion channels, we present the development of two-dimensional Ti3C2Tx ion nanochannels incorporating 4-aminobenzo-15-crown-5-ether molecules as specific ion binding sites. These binding sites had a significant influence on the ion transport process and improved ion recognition. Permeation of both Na+ and K+ was facilitated because their ion diameters are compatible with the cavity in the ether ring. Moreover, owing to the strong electrostatic interactions, the permeation rate for Mg2+ increased by a factor of 55 compared to that for the pristine channels, which was higher than those of all monovalent cations. Furthermore, the transport rate for Li+ was relatively lower than those of Na+ and K+, which was attributed to difficult binding of the Li+ to the oxygens in the ether ring. Consequently, the ion selectivities of the composite nanochannel were up to 7.6 for Na+/Li+ and 9.2 for Mg2+/Li+. Our work presents a straightforward approach to creating nanochannels exhibiting precise ion discrimination.
We report on the surface and bulk chemistry of LixMn2O4 (0 < x < 1) spinel oxide electrode for the selective extraction of LiCl from natural salt lake brines using an electrochemical method based on LiMn2O4 (LMO) lithium intercalation electrode and polypyrrole (PPy) reversible chloride electrode. Both the surface composition and insertion/release of Li-ions into/from the crystal structure have been studied with pulsed laser deposited (PLD) thin LixMn2O4 films and composite LMO/carbon black electrodes. Cyclic voltammetry, XPS/UPS, XRD, chrono-amperometry, and galvanostatic intermitent transient titration (GITT) experiments in model LiNO3 solutions and natural brines from Salar de Olaroz (Jujuy, Argentina) have been used. Repetitive CV and GITT experiments showed reversible extraction/intercalation of Li-ions in LMO with high selectivity and electrode stability in natural brine while PPy is reversible to chloride ions. Chronoamperometry for time bound diffusion in small nanocrystals with interference of concentration profiles yielded DLi+ 10-10 cm-2.s-1. Photoelectron spectroscopy showed Mn/O surface stoichiometry close to 1:2 and initial 1:1 MnIV/MnIII ratio with MnIII depletion during oxidation at 1.1 V vs. Ag/AgCl and recovery of surface MnIII after reduction at 0.4 V. Co-adsorption of Na+ was detected which resulted in slower ion exchange of Li-ions but there was no evidence of Na+ intercalation in the Mn oxide electrode.
This article describes the gelation by PVC of supported liquid membranes (SLMs) for nitrate removal using a quaternary ammonium salt as carrier. Untreated SLMs with this carrier are very unstable. To improve their stability, the LM-phase was gelled with polyvinyl chloride as gel-forming polymer. Both homogeneous gelations of the LM-phase as well as the application of an interfacial gel layer are described. In all cases, no improvement of the stability could be observed. For both types of gelation, the initial nitrate flux decreased while the flux after 1 day of degradation was almost zero. The flux decrease is the result of a decrease of the diffusion rate of carrier complex as a result of the presence of the gel network and the thickness of the applied gel layer. The absence of any stability improvement might indicate that the loss of LM-phase from these membranes is due to dissolution of carrier or membrane solvent and not a result of emulsion formation only. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1205–1216, 1997
The details of the ion exchange properties of layered H2TiO3, derived from the layered Li2TiO3 precursor upon treatment with HCl solution, with lithium ions in the salt lake brine (collected from Salar de Uyuni, Bolivia) are reported. The lithium adsorption rate is slow, requiring 1 d to attain equilibrium at room temperature. The adsorption of lithium ions by H2TiO3 follows the Langmuir model with an adsorptive capacity of 32.6 mg g(-1) (4.7 mmol g(-1)) at pH 6.5 from the brine containing NaHCO3 (NaHCO3 added to control the pH). The total amount of sodium, potassium, magnesium and calcium adsorbed from the brine was <0.30 mmol g(-1). The H2TiO3 was found capable of efficiently adsorbing lithium ions from the brine containing competitive cations such as sodium, potassium, magnesium and calcium in extremely large excess. The results indicate that the selectivity order Li(+) ≫ Na(+), K(+), Mg(2+), Ca(2+) originates from a size effect. The H2TiO3 can be regenerated and reused for lithium exchange in the brine with an exchange capacity very similar to the original H2TiO3.
A salinity gradient solar pond (SGSP) is a simple and effective way of capturing and storing solar energy. The Qinghai-Tibet Plateau has very good solar energy resources and very rich salt lake brine resources. It lacks energy for its mineral processes and is therefore an ideal location for the development and operation of solar ponds. In China, solar ponds have been widely applied for aquaculture, in the production of Glauber’s salt and in the production of lithium carbonate from salt lake. As part of an experimental study, a SGSP using the natural brine of Zabuye salt lake in the Tibet plateau has been constructed. The pond has an area of 2500m2 and is 1.9m deep. The solar pond started operation in spring when the ambient temperature was very low and has operated steadily for 105days, with the LCZ temperature varying between 20 and 40°C. During the experimental study, the lower convective zone (LCZ) of the pond reached a maximum temperature of 39.1°C. The results show that solar ponds can be operated successfully at the Qinghai-Tibet plateau and can be applied to the production of minerals.
The authors have carried out scientific investigations of salt lakes on the Qinghai-Tibet Plateau since 1956 and collected 550 hydrochemical data from various types of salt lakes. On that basis, combined with the tectonic characteristics of the plateau, the hydrochemical characteristics of the salt lakes of the plateau are discussed. The salinity of the lakes of the plateau is closely related to the natural environment of lake evolution, especially the climatic conditions. According to the available data and interpretation of satellite images, the salinity of the lakes of the plateau has a general trend of decreasing from north and northwest to south and southeast, broadly showing synchronous variations with the annual precipitation and aridity (annual evaporation/annual precipitation) of the modern plateau. The pH values of the plateau salt lakes are related to both hydrochemical types and salinities of the lake waters, i.e., the pH values tend to decrease from the carbonate type → sodium sulfate subtype → magnesium sulfate subtype → chloride type; on the other hand, a negative correlation is observed between the pH and salinities of the lakes. Geoscientists and biological limnologists generally use main ions in salt lakes as the basis for the hydrochemical classification of salt lakes. The common ions in salt lakes are Ca2+, Mg2+, Na+, K+, Cl− SO42−, CO32−, and HCO3−. In this paper, the Kurnakov-Valyashko classification is used to divide the salt lakes into the chloride type, magnesium sulfate subtype, sodium sulfate subtype and carbonate type, and then according to different total alkalinities (K
C = Na2CO3 + NaHCO3/total salt × 100%) and different saline mineral assemblages, the carbonate type is further divided into three subtypes, namely, strong carbonate subtype, moderate carbonate subtype and weak carbonate subtypes. According to the aforesaid hydrochemical classifications, a complete and meticulous hydrochemical classification of the salt lakes of the plateau has been made and then a clear understanding of the characteristics of N–S hydrochemical zoning and E-W hydrochemical differentiation has been obtained. The plateau is divided into four zones and one area. There is a genetic association between certain saline minerals and specific salt lake hydrochemical types: the representative mineral assemblages of the carbonate type of salt lake is borax (tincalconite) and borax-zabuyelite (L2CO3) and alkali carbonate-mirabilite; the representative mineral assemblages of the sodium sulfate subtype are mirabilite (thenardite)-halite and magnesium borate (kurnakovite, inderite etc.)-ulexite-mirabilite; the representative mineral assemblages of the magnesium sulfate subtype are magnesium sulfate (epsomite, bloedite)-halite, magnesium borate-mirabilite, and mirabilite-schoenite-halite, as well as large amount of gypsum; The representative mineral assemblages of the chloride type are carnallite-bischofite-halite and carnallite-halite, with antarcticite in a few individual salt lakes. The above-mentioned salt lake mineral assemblages of various types on the plateau have features of cold-phase assemblages. Mirabilite and its associated cold-phase saline minerals are important indicators for the study of paleoclimate changes of the plateau. A total of 59 elements have been detected in lake waters of the plateau now, of which the concentrations of Na, K, Mg, Ca, and Cl, and SO42−, CO32−, and HCO3− ions are highest, but, compared with the hydrochemical compositions of other salt lake regions, the plateau salt lakes, especially those in the southern Qiangtang carbonate type subzone (I2), contain high concentrations of Li, B, K, Cs, and Rb, and there are also As, U, Th, Br, Sr, and Nd positive anomalies in some lakes. In the plateau lake waters, B is intimately associated with Li, Cs, K and Rb and its concentration shows a general positive correlation with increasing salinity of the lake waters. The highest positive anomalies of B, Li, Cs, and K center on the Ngangla Ringco Lake area in the western segment of the southern Qiangtang carbonate type subzone (I2) and coincide with Miocene volcanic-sedimentary rocks and high-value areas of B, Li, and Cs of the plateau. This strongly demonstrates that special elements such as B, Li, and Cs on the plateau were related to deep sources. Based on recent voluminous geophysical study and geochemical study of volcanic rocks, their origin had close genetic relation to anatectic magmatism resulting from India–Eurasia continent–continent collision, and B–Li (-Ce) salt lakes in the Cordillera Plateau of South America just originated on active continental margins, both of which indicate that global specific tectonically active belts are the main cause for the high abundances of B, Li, and Cs (K and Rb) in natural water and mineralization of these elements.
Technological improvements in rechargeable solid-state batteries are being driven by an ever-increasing demand for portable electronic devices. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. We present a brief historical review of the development of lithium-based rechargeable batteries, highlight ongoing research strategies, and discuss the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems.
The nearby brown dwarf LP 944-20 has been monitored for radial velocity variability at optical and near-infrared wavelengths using the VLT/UVES and the Keck/NIRSPEC, respectively. The UVES radial velocity data obtained over 14 nights spanning a baseline of 841 days show significant variability with an amplitude of 3.5 km s-1. The periodogram analysis of the UVES data indicates a possible period between 2.5 and 3.7 hr, which is likely due to the rotation of the brown dwarf. However, the NIRSPEC data obtained over 6 nights show an rms dispersion of only 0.36 km s-1 and do not follow the periodic trend. These results indicate that the variability seen with UVES is likely to be due to rotationally modulated inhomogeneous surface features. We suggest that future planet searches around very low mass stars and brown dwarfs using radial velocities will be better conducted in the near-infrared than in the optical.
Loss of organic extraction in membrane extraction process could be avoided by using an ion permeable, solvent stable barrier membrane. Development of solvent stable materials has been a key issue for liquid-liquid membrane extraction. A new type of solvent resistant membrane, prepared from block copolymer poly (ethylene-co-vinyl alcohol) (EVAL) via immersion precipitation, is introduced as the barrier in membrane extraction of lithium from a real salt lake brine. The influence of EVAL concentration on the casting solution viscosity and the membrane properties was investigated. The membranes were characterized by scanning electron microscopy (SEM), water uptake, pure water flux, mechanical strength, and Li þ diffusion flux. Membrane phase separation was conducted at a temperature below the crys-tallization temperature of the polymer to ensure suitable membrane structure. The membrane prepared from 30 wt% EVAL content showed a Li þ flux of 2.7 Â 10 À 8 mol cm À 2 s À 1 at a Li þ feed concentration of 0.1 mol/L in a diffusion test. Using a tributylphosphate (TBP)/kerosene extractant, the lithium flux in a membrane extraction showed a linear relationship with the feed lithium concentration. In addition, long term stability tests showed a stable lithium extraction flux for about 1037 h. These results indicate that EVAL material is a promising stabilizing barrier membrane in liquid-liquid extraction of lithium.
Lithium recovery from salt lake brine with a high magnesium/lithium concentration ratio from Qinghai province, China, was investigated. Li+ extraction was performed using tributyl phosphate in methyl isobutyl ketone as the extractant and FeCl3 as the coextractant. An extraction mechanism, based on cation exchange of Li+ and Mg2 + with H+ and Na+, was proposed. Boron exists as B(OH)4− in salt lake brine and is extracted into organic phase as boric acid. B(OH)4− in salt lake brine can strip H+ from the regenerated organic phase; this results in extraction of larger amounts of Li+ and Mg2 + because of electroneutrality. Based on cation exchange mechanism and neutralization of B(OH)4− with H+, the extraction behaviors of Li+ and Mg2 + from salt lake brine are successfully predicted. An experiment using a five-stage mixer-settler with countercurrent flow was conducted. The results showed that B(OH)4− largely favors lithium extraction from salt lake brine.
Recovery of lithium ions from salt lake brine is becoming more important because of the rapid increase in projected demand for lithium resources. N,N-bis(2-ethylhexyl)acetamide (N523) is a newly developed extractant that presents good lithium extraction ability and selectivity. In this study, the kinetics and mechanism of lithium ion extraction with N523 in kerosene at 298.15 K were investigated using the rising single drop method. Results showed that the extraction process is controlled by diffusion and that the chemical reaction occurs at the interfacial area.
Uptake of lithium ion from brine on ion-sieve spinel-type adsorbents (H1.33Mn1.67O4 and H1.6Mn 1.6O4) was studied batchwise. The adsorbents exhibited extremely high affinity toward lithium ion in brine (NaHCO3 added to control pH) with lithium uptake capacity of 27-30mg g-1 at pH 6.6.
Abstract H2TiO3-lithium adsorbent was obtained from the acid-modified precursor Li2TiO3, which was synthesized via the solid-phase reaction between LiOH·H2O and a Ti-rich material. The Ti-rich material containing 88.35% TiO2 was prepared from low-grade titanium slag via an upgrading process primarily involving alkaline roasting and acid leaching-hydrolysis. The parameters for the synthesis and acid treatment of the Li2TiO3 precursor were investigated. It was observed that monoclinic β-Li2TiO3 with good crystallization could be synthesized at 750 °C with a Li/Ti molar ratio of 2.5. The adsorbent obtained under the optimized preparation conditions exhibited an excellent lithium adsorption capacity of up to 27.8 mg/g in LiOH solution with a Li+ concentration of 2 g/L, and the adsorption capacity stabilized at 23 to 24 mg/g after several cycles. The adsorbent had better Li+ selectivity in the synthetic salt-lake brine solution. The separation coefficients of Li+ to Na+ and K+ reached 37.5 and 26.9, respectively.
Extraction of lithium from brine is becoming a focus of importance worldwide. Lithium was extracted from brine by membrane electrolysis in this paper, and the influences of operating parameters on Li+ exchange capacity and stability of electrode are investigated. Various parameters including initial lithium concentration of anolyte, anode-cathode distance, electrolyte temperature, surface density of active substrate and electrolysis time are optimized. Under the optimal conditions, the electrode exhibits a remarkable Li+ exchange capacity of 38.9mg/g and the pH value of anolyte is less than 8. The results are beneficial for the extraction of lithium from brine by membrane electrolysis.
Owing to the high ratio of Mg2+ to Li+ in most of the salt lake brines in China, it is difficult to extract lithium. Therefore, the separation efficiency of a nanofiltration membrane was investigated in this study. Operating conditions such as operating pressure, inflow water temperature, pH, and Mg2+/Li+ ratio were investigated. Relationship between the rejection rates of magnesium and lithium was established. Moreover, the extractions of lithium from salt lake brines were also evaluated. The results indicate that the separation of magnesium and lithium was highly dependent on the Mg2+/Li+ ratio, operating pressure, and pH. When the Mg2+/Li+ ratio was <20, the competitive coefficient was sensitive to the Mg2+/Li+ ratio. The permeate flux of membrane for the East Taijiner brine was higher than that for the West Taijiner brine.
The availability and sustainable supply of technology metals and valuable elements is critical to the global economy. There is a growing realization that the development and deployment of the clean energy technologies and sustainable products and manufacturing industries of the 21st century will require large amounts of critical metals and valuable elements including rare-earth elements (REEs), platinum group metals (PGMs), lithium, copper, cobalt, silver and gold. Advances in industrial ecology, water purification and resource recovery have established that seawater is an important and largely untapped source of technology metals and valuable elements. This feature article discusses the opportunities and challenges of mining critical metals and elements from seawater. We highlight recent advances and provide an outlook of the future of metal mining and resource recovery from seawater.
Kaolin, talc powder and alumina were used as raw materials to prepare ceramic foams using a protein foaming agent via direct foaming. CH3COOLi and Ti(OC4H9)4 were employed as lithium and titanium sources, respectively to synthesize Li2TiO3 by the sol-gel process during which Li2TiO3 was loaded on ceramic foams to address the problem that powdery Li2TiO3 is difficult to be used in extracting lithium directly from the sea water and salt lake brine for engineering troubles. Hydrochloric acid was used to treat Li2TiO3 to obtain H2TiO3-lithium adsorbent. The results indicate that ceramic foams with a high open porosity are observed, and Li2TiO3 with particle size 80-100 nm is loaded on ceramic foams successfully. The Li+ drawn out ratio from Li2TiO3 reaches 50.2%, and the adsorptive capacity comes up to 21.0 mg g−1 after a treatment 24 h.
This review will examine the most recent research and developments in hollow fibre contactor technology and membrane-based extraction processes, including the latest improvements with regard to stability and flux. The described classification attempts to cover all studies performed by means of non-dispersive contact using hydrophilic/hydrophobic microporous polymeric supports, either by impregnating the membrane or filling its pores with the bulk of the aqueous/organic solution. All membrane processes covered under these categories will be compared with improved versions in terms of performance, mass transfer modelling, stability issues, applications and the state of the art in membrane-based separation techniques. In general, an attempt will be made to review the literature published between 2005 and 2012 (August 2012) in order to focus on the real status of hollow fibre technology and membrane-based extraction processes. In a modern approach, the prospects for the use of ionic liquid (IL) as a membrane carrier for different applications with different membrane morphologies are also presented. In addition, new highly stabilised techniques developed by different researchers, such as hollow fibre renewal liquid membranes (HFRLMs) and pseudo-emulsion-based hollow fibre strip dispersion (PEHFSD), are also discussed.
The ion exchange process was employed to recover lithium from brine collected from Urmia lake Iran, which contains saturated levels of Na, Mg, K and low Li (2.45 mmol.L− 1 or 17 mg.L− 1). The high levels of these impurities in Urmia Lake would create difficulties during lithium processing if conventional techniques were used. To this end, the spinel-type MnO2 nanorod, with the size about 40–90 nm in diameter and 150–900 nm in length, was first synthesized as a lithium ion sieve via a hydrothermal method. The lithium uptake capacity of this synthesized ion sieve reached to 9 mmol.g− 1, which is the maximum value among the adsorbents studied to date. The crystalline structure, property and size of all products involving oxidizer, precursor and ion sieve are examined via powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Also the lithium selective adsorption property was investigated by measuring the distribution coefficients (Kd) of a series of alkaline and alkaline–earth metal ions, which is significant for lithium extraction from aqueous solutions with very low lithium content. Furthermore, the results show that the synthesized MnO2 nanorods could be utilized in lithium extraction from Urmia Lake brine and other environment including sea water and waste water.
We demonstrate fast and efficient chemical redox insertion of lithium ions into solid FePO4 from lithium salt solutions contaminated with other cations. The method is illustrated with sodium thiosulfate, Na2S2O3, as a reducing agent that is found to have an optimum redox potential for this reaction. The method shows a very high selectivity for lithium extraction; enrichment in lithium concentration vs. other ions of more than 500 is achieved under the conditions relevant to lithium extraction from brines.
To investigate the feasibility of a novel method to produce LiOH from lithium contained brine, A lab-scale electro–electrodialysis with bipolar membrane (EEDBM) was installed with an arrangement of bipolar membrane–cation exchange membrane–bipolar membrane–cation exchange membrane in series. Conventional electrodialysis (CED) stack configured with repeat-arranged five cation exchange membranes and four anion exchange membranes was installed as a pretreatment process. After preconcentrating and precipitating brine with CED and Na2CO3, a high purity of ca. 98% Li2CO3 powder was obtained. The influence of current density and feed concentration on the production of LiOH was investigated. EEDBM Process cost is estimated to 2.59 $/kg at current density of 30 mA/cm2 and feed concentration of 0.18 M. It can be inferred that lower energy consumption would be obtained at the case of scaling up. Considering the environmental aspects, the corporate process for LiOH production is also mutually beneficial.
To explore the feasibility of extracting lithium metal from brine sources, three salts, MgCl2, CaCl2, and NH4Cl, were selected as chloride sources, and the extraction equilibrium of lithium was studied with tributyl phosphate (TBP) in kerosene and FeCl3 as a coextracting agent at different values of Fe/Li. The extraction mechanism for lithium with TBP in kerosene and FeCl3 as a coextracting agent was investigated too. The results showed that the extraction of the lithium ion is a cation-exchange reaction, and the extraction of iron ion is the precondition of the extraction of lithium ion. All of the extractability of the iron ion increased with the chloride concentration with MgCl2, CaCl2, and NH4Cl as chloride sources, and the extraction capacity of lithium ion followed the sequence: MgCl2 > CaCl2 > NH4Cl, with recoveries from MgCl2 as chloride sources being much higher than that for CaCl2 and NH4Cl as chloride sources at all values of Fe/Li. There exists competitiveness between Li+ and NH4+, Ca2+, and Mg2+ when combined to TBP and FeCl3 and a salting-out effect of three salts. MgCl2 benefits from weaker competitiveness and a stronger salting-out effect than the other two. Choosing MgCl2 as chloride sources at Fe/Li = 1.9 obtains the highest partition coefficient with TBP/kerosene as an extractant and FeCl3 as a coextracting agent.
Lithium recovery from salt-lake brines was explored using the extraction equilibria of lithium with tributyl phosphate (TBP) in methyl isobutyl ketone (MIBK), with FeCl3 coextractant, for various volume concentrations of TBP, molar ratios of Fe to Li, and volume ratios of the organic to aqueous phases. Washing and stripping equilibria of magnesium and lithium ions with HCl, NH4Cl, and LiCl/HCl and NH4Cl/HCl combinations were investigated. The extraction of lithium ions from salt-lake brines was successful. NH4Cl was a suitable washing agent for magnesium ions but not for stripping lithium ions into the aqueous phase. HCl can wash magnesium ions and strip lithium ions but corrodes equipment. The LiCl/HCl and NH4Cl/HCl combinations reduced equipment corrosion and washed and stripped magnesium and lithium ions, respectively, at appropriate volume ratios. MIBK loss was reduced using high-salinity solutions and large volume ratios during extraction and adjusting the volume ratio and overall chloride-ion concentration during washing/stripping.
The demand for lithium will increase in the near future to 713,000 tonnes per year. Although lake brines contribute to 80% of the production, existing methods for purification of lithium from this source are expensive, slow, and inefficient. A novel electrochemical process with low energy consumption and the ability to increase the purity of a brine solution to close to 98% with a single-stage galvanostatic cycle is presented.
The challenge for lithium extraction from brine has been the separation of Mg and Li. Because they are located in diagonal positions within the periodic table, they exhibit many chemical similarities. But since Mg2 + has a high charge density and is easily hydrated, we explored a new separation method from an electrochemical perspective using LiFePO4/FePO4 as electrode materials. Through CV tests and technical experiments in a different electrolyte, this approach was verified. Our results show that lithium exhibits good reversibility in LiFePO4/FePO4 structures, and the redox peak separation is 0.592 V while that of Mg2 + is 1.403 V, indicating its more serious polarization. Technical studies using a voltage of 1.0 V show that, in pure lithium solution, the inserted capacity of lithium can reach 41.26 mg · (1 g LiFePO4)− 1, which is 93.78% of its theoretical value (44 mg), and the subsequent extracted capacity can attain 38.93 mg · (1 g LiFePO4)− 1, which is 94.3% of its inserted capacity. But the extracted capacity of Mg2 + from a solution containing magnesium is only 5.5 mg · (1 g LiFePO4)− 1. Furthermore, the experimental data at different voltages prove that a lower voltage is beneficial for separating Mg and Li, and this method also works well in brine since the Mg/Li ratio can be reduced to 0.45 from 60. All these results indicate that this method, while simple, is quite promising for separating Mg and Li from a high Mg/Li ratio brine.
Previous studies of the availability of lithium for use in batteries to power electric vehicles (EVs) have reached the generally encouraging conclusion that resources are sufficient to meet growing demand for the remainder of the 21st century. However, these surveys have not looked past estimates of lithium resource to the geological constraints on deposit size and composition that will allow the resources to be converted to reserves from which lithium can be produced economically. In this survey, we review the relevant geological features of the best characterized pegmatite, brine and other types of lithium deposits and compare their potential for large-scale, long-term production.
The separation of calcium and magnesium from lithium chloride solution by liquid-liquid extraction with di (2-ehtylhexyl) phosphoric acid was studied and the influence of time, concentration, pH and temperature on the extraction was investigated. Using the extraction isotherms, the number of theoretical stages and the dependence on the phase flow ratio of organic to aqueous phase were determined. A total of 99% of the calcium and magnesium are separated from lithium using 0.5 M solution of the extractant dissolved in paraffin oil in two extraction stages with a phase ratio of Vorg/Vw 1:3 at room temperature. The losses of the extractant during the extraction process were determined.
Lithium has been removed electrochemically at 15 μA/cm2 from LiMn2O4 (spinel) to yield single phase Li1−xMn2O4 for 0 < × ⩽ 0.60. The electrochemical curve suggests that beyond x = 0.60 an electrochemical process other than lithium extraction occurs. Powder X-ray-diffraction spectra indicate that during the extraction process the [Mn2]O4 framework of the spinel structure remains intact. Previous results have shown that 1.2 Li+ ions can also be inserted into LiMn2O4, which suggests that lithium may be cycled in and out of the [Mn2]O4 framework of the spinel structure over a wide range of x, at least from Li0.4Mn2O4 to Li2Mn2O4. Discussion of the mechanism of formation of λ-MnO2 in an acidic environment is extended.
Lithium was selectively extracted from near-neutral aqueous solutions of alkali metal salts. The mechanism by which this was achieved involves the formation of the trioctylphosphine oxide adduct of a lithium chelate of a fluorinated β-diketone, which is then readily extractable into an organic diluent. High separation factors were obtained from sodium, potassium, rubidium, and cesium. The selectivity of the fluorinated β-diketones for lithium over the alkaline earths was found to be poor. A suggested general flowsheet for the recovery of lithium from a salt brine concentrate is included.
Abstract Investigations on stratigraphy, geomorphology and neotectonic movement in the Eastern Kunlun Mountains show that there existed a series of ancient lakes, including some saline lakes, in the studied region about 30,000 years ago. They were distributed south of the middle Kunlun fault, from the middle-upper reaches of the present Narin Gol River in the west to the Alag Lake-Tosou Lake in the east. Of these the ancient Narin Gol Lake and Kunlun Lake were mainly recharged by the hot water related to valcanos, so the B, Li and K contents are relatively high.
The neotectonic movement that commenced at 30,000 a B.P. caused the river system in the Eastern Kunlun Mountains to invade southwards; as a result the ancient lake water was captured to recharge the Qarhan area. Therefore, the hot springs related to recent volcanism and faulting on the southern bank of the upper reaches of the Narin Gol River became an important source of saline materials for the Qarhan Lake.
Lithium chloride extraction with n-butanol has been studied using synthetic solutions containing different quantities of lithium chloride, sodium chloride, potassium chloride and calcium chloride. Based on distribution coefficients, separation factors and McCabe-Thiele representation of the results, a process has been proposed for separation and recovery of lithium chloride. This process has been successfully applied for production of lithium chloride from leach solutions at the laboratory scale. The purity of this lithium chloride product was as high as 99.6%.
Annular centrifugal extractors (ACE), based on the principle of Taylor-Couette flow, offer potential advantages over the existing conventional extraction equipments in many of the engineering applications. In the present work, dispersed phase hold-up (is an element of(D)) and effective interfacial area ((a) under bar) have been measured in 30, 75 and 250 mm rotor diameter annular centrifugal extractors over a wide range of power consumption (0.4 < P/V < 500, kW/m(3)) and physical properties (900 < rho
The Li+ uptake was studied by two lithium ion-sieves with different properties (surface, crystal configuration, and grain size). The reaction of Li+ uptake was investigated in batch experiments via the pH technique. Equilibrium studies were performed in solution pH 7, 10, 12 and the Langmuir equation was applied to the data. The results indicated that there was strong responsive behavior of Li+ uptake to pH in neutral or weak alkaline solutions, and Li+ uptake could not proceed completely for reason of pH descent with proton releasing from ion-sieves. Sieve-2 had faster Li+ uptake rate than Sieve-1 owing to the quicker intraparticle diffusion in the small grain. The Li+–H+ ion-exchange was accepted as the main mechanism of Li+ uptake by spinel-type manganese oxide with manganese valence nearly equals to +4. Furthermore, it suggested that Li+ uptake by ion-sieves would be necessary to study in buffer solution.
The cubic phase LiMn2O4 spinel is synthesized via a directly soft chemistry method via hydrothermal reaction of Mn(NO3)2, LiOH and H2O2 at 383K for 5–10h, more favorable to control the nanocrystalline structure with well-defined pore-size distribution and high surface area than traditional solid-phase reaction at high temperature. Further, the 1D MnO2 nanorod ion-sieves with lithium ion selective adsorption property is prepared by the acid treatment process to completely extract lithium ions from the LiMn2O4 lattice. The effects of hydrothermal conditions on the nanostructure, chemical stability and ion-exchange property of the LiMn2O4 spinel and MnO2 ion-sieve are examined via powder X-ray diffraction (XRD), N2 adsorption–desorption at 77K, high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED) and lithium ion selective adsorption measurements. The results show that the 1D MnO2 nanorods might be utilized in lithium extraction from aqueous environment including brine, seawater and waste water.
Here, we report a new battery capable of efficiently recovering lithium from brines that is composed of a lithium-capturing cationic electrode (LiFePO4) and a chloride-capturing anionic electrode (Ag). It can convert a sodium-rich brine (Li : Na = 1 : 100) into a lithium-rich solution (Li : Na = 5 : 1) by consuming 144 W h per kg of lithium recovered.
Lithium is a highly interesting metal, in part due to the increasing interest in lithium-ion batteries. Several recent studies have used different methods to estimate whether the lithium production can meet an increasing demand, especially from the transport sector, where lithium-ion batteries are the most likely technology for electric cars. The reserve and resource estimates of lithium vary greatly between different studies and the question whether the annual production rates of lithium can meet a growing demand is seldom adequately explained. This study presents a review and compilation of recent estimates of quantities of lithium available for exploitation and discusses the uncertainty and differences between these estimates. Also, mathematical curve fitting models are used to estimate possible future annual production rates. This estimation of possible production rates are compared to a potential increased demand of lithium if the International Energy Agency's Blue Map Scenarios are fulfilled regarding electrification of the car fleet. We find that the availability of lithium could in fact be a problem for fulfilling this scenario if lithium-ion batteries are to be used. This indicates that other battery technologies might have to be implemented for enabling an electrification of road transports.
The demand for lithium has greatly increased with the rapid development of rechargeable batteries. Currently, the main lithium resource is brine lakes, but the conventional lithium recovery process is time consuming, inefficient, and environmentally harmful. Rechargeable batteries have been recently used for lithium recovery, and consist of lithium iron phosphate as a cathode. These batteries feature promising selectivity between lithium and sodium, but they suffer from severe interference from coexisting magnesium ions, an essential component of brine, which has prompted further study. This study reports on a highly selective and energy-efficient lithium recovery system using a rechargeable battery that consists of a λ-MnO2 positive electrode and a chloride-capturing negative electrode. This system can be used to recover lithium from brine even in the presence of magnesium ions as well as other dissolved cations. In addition, lithium recovery from simulated brine is successfully demonstrated, consuming 1.0 W h per 1 mole of lithium recovered, using water similar to that from the artificial brine, which contains various cations (mole ratio: Na/Li ≈ 15.7, K/Li ≈ 2.2, Mg/Li ≈ 1.9).
New materials hold the key to fundamental advances in energy conversion and storage, both of which are vital in order to meet the challenge of global warming and the finite nature of fossil fuels. Nanomaterials in particular offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. This review describes some recent developments in the discovery of nanoelectrolytes and nanoelectrodes for lithium batteries, fuel cells and supercapacitors. The advantages and disadvantages of the nanoscale in materials design for such devices are highlighted.
To explore the feasibility of extracting lithium metal from brine sources, three salt solutions, FeCl3, ZnCl2, and CrCl3, were selected as coextracting agents, and the extraction equilibrium of lithium was studied with tributyl phosphate (TBP) in kerosene, TBP in methyl isobutyl ketone (MIBK), and TBP in 2-octanol. The results showed that the extraction capacity followed the sequence: TBP/MIBK > TBP/kerosene > TBP/2-octanol, with recoveries from the TBP/MIBK and TBP/kerosene systems being much larger than that for TBP/2-octanol with FeCl3 solution as the coextracting agent. The third phase was found for the TBP/kerosene system with FeCl3 solution as the coextracting agent at a low volume concentration of TBP, which did not appear for other systems at all volume concentrations. Synergistic extraction exists between TBP and MIBK, and the weak hydrogen bond association exists between −OH in 2-octanol and −P═O in TBP. The coextracting capacity for FeCl3 was much larger than that for ZnCl2 and CrCl3, and that for TBP/2-octanol with CrCl3 was a little larger than that for others.
Spinel-type lithium antimony manganese oxide was ®rst synthesized by aging the precipitates that were
obtained by reaction of a mixed aqueous solution of manganese(II) and antimony(V) chlorides (Sb/Mn~0.25) with (LiOH.H2O2) solution, followed by hydrothermal treatment at 120 C. A well crystallized spinel-type solid with a chemical composition of Li1.16Sb(V)0.29Mn(III)0.77Mn(IV)0.77O4 was obtained; it had the characteristic of including mixed valence manganese. The spinel structure was preserved during heating up to 600 C. Most of the lithium ions in the prepared material could be extracted by treating with an acid; the extraction progressed topotactically, preserving the spinel structure, accompanied by a decrease in the lattice constant from 8.31 A to 8.13 A . The mean oxidation of manganese increased from 3.50 to 3.98 after acid treatment, due to the disproportionation of trivalent manganese. The DTA-TG analysis and IR spectra showed the formation of lattice protons exchangeable with lithium ions. The pH titration study showed that the acid treated sample had a remarkable lithium ion-sieve property over the entire pH range studied. The affinity order was K < Na <<Li and the exchange capacity reached 5.6 mmol/g for Li. It showed a selective uptake of 14 mg/g of Li from LiCl enriched seawater.
Magnesium (II) doped spinel lithium manganese oxide (LMS) was synthesized by soft chemical method and nanosized ion sieve manganese oxide (HMS) was prepared by extracting lithium and magnesium from LMS. The characteristics of HMS were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, surface areas and determination of pH at the point of zero charge. Experiments were performed to study the effects of pH, adsorbent dose, contact time and Li+ concentration. The competitive model was used to describe the competition between Li+–H+ and the applicability of different kinetic models was evaluated. The results showed that the pH at the point of zero charge of HMS was about 7.8. The recycle of HMS explained that it could be used as Li+ adsorbent with topotactical extraction of lithium. Under optimized batch conditions up to 99.2% Li+ could be recovered from solution within 24 h. The adsorption process followed the pseudo-second-order model and followed an intraparticle diffusion model at the beginning.
Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.
The increasing interest in energy storage for the grid can be attributed to multiple factors, including the capital costs of managing peak demands, the investments needed for grid reliability, and the integration of renewable energy sources. Although existing energy storage is dominated by pumped hydroelectric, there is the recognition that battery systems can offer a number of high-value opportunities, provided that lower costs can be obtained. The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.
- H Chitrakar
- Y Kanoh
- Y Makita
- K Miyai
- Ooi
Chitrakar, H. Kanoh, Y. Makita, Y. Miyai and K. Ooi,
J. Mater. Chem., 2000, 10, 2325-2329.
- W Tian
- M Ma
- Han
Tian, W. Ma and M. Han, Chem. Eng. J., 2010, 156, 134-140.
- S Zhang
- S Li
- X Sun
- J Yin
- Yu
Zhang, S. Li, S. Sun, X. Yin and J. Yu, Chem. Eng. Sci.,
2010, 65, 169-173.