No full-text available
To read the full-text of this research,
you can request a copy directly from the authors.
Advance review on the exploitation of the prominent energy-storage element: Lithium. Part I: From mineral and brine resources
Abstract
Lithium (Li), an exceptional cathode material in rechargeable batteries, is an essential element in modern energy production and storage devices. The continuously increasing demand for lithium in these devices, along with their steady production, has led to the high economic importance of lithium, making it one of the strategically influential elements. The uneven distribution of mineral resources in the earth’s crust and the unequal concentration in brine and sea water reserves also causes lithium exploitation to be of critical importance. This situation requires the efficient processing of lithium resources either by the processing of minerals/brine/sea water or by the recycling of spent lithium-ion batteries. To explore new routes for the sustainable exploitation of lithium, it is imperative to review the methodologies that have already been studied and are currently in industrial practice. In this study, we present an overview of the processes investigated for the extraction, separation and recovery of lithium from not only a technological perspective but also from a chemical perspective.
... Li is sourced from solid materials such as ores and clays, as well as liquid sources including brine, seawater, and oil fields. The industry primarily uses salt lake brine, geothermal brines, and spent Li electrolytes among liquid sources (Choubey et al., 2016;Zavahir et al., 2021). In particular, continental brine constitutes 59% of the global Li reserves (Krebs, 2006;Swain, 2017). ...
... Although seawater holds about 230 billion tons of Li, its low concentration range of 0.1-0.2 ppm makes extraction economically unfeasible (Choubey et al., 2016;Grosjean et al., 2012;Li et al., 2018). Current research, therefore, focuses more on extracting Li from salt lake brine, as geothermal brine poses challenges due to the presence of other cations. ...
... Despite having a high recovery rate, the process has failed to draw significant attention from researchers due to the following reasons: (i) the use of highly toxic chlorine gas, (ii) high maintenance cost due to corrosion, and (iii) mass loss due to the volatile nature of LiCl and associated ore-impurity chlorides. 3,63,64 Despite its shortcomings, the highly selective nature of chlorine results in a high recovery of minerals from ores especially from lowprofile ores. Further to this, the vapor pressure difference of the formed impurity chlorides can result in a high recovery of waste. ...
... In this way, not only the direct application of toxic HF was avoided but also the requirement of a high temperature by conventional H 2 SO 4 process was minimized. Other acids such as HNO 3 and HCl are also used for Li recovery. 87−89 Zhu et al. reported a comparison between the extraction efficiency of H 2 SO 4 and HCl. ...
... [10,11] Lepidolite is composed of two tetrahedral SiO 4 sheets with sandwiched octahedral [AlO 6 ] sheet, where the Al can be replaced with Li, and high roasting temperatures are required to release the Li + . [10,12,13] Beyond these specific considerations mentioned, more generally the processes for Li + extraction are similar and involve unit operations of calcination, leaching, precipitation, and purification. [10,14] The various processing techniques to extract Li + from ores include acid or alkali treatment, salt roasting, and chlorination. ...
... [10,14] The various processing techniques to extract Li + from ores include acid or alkali treatment, salt roasting, and chlorination. [10,11,13] For the final Li + purification step, the Li + is usually precipitated using sodium carbonate and then further purified to battery-grade Li 2 CO 3 . [11] Among all these methods, the energy consumption and cost of using acid methods were higher than the alkali methods because the alkali methods have a simplified leaching purification process and reduced consumption of chemicals and energy. ...
Worldwide lithium demand has surged in recent years due to increased production of Li‐ion batteries for electric vehicles and stationary storage. Li supply and production will need to increase such that the transition towards increased electrification in the energy sector does not become cost prohibitive. Many countries have taken policy steps such as listing Li as a critical mineral. Current commercial Li mining is mostly from dedicated mine sources, including ores, clays, and brines. The conventional ways to extract Li⁺ from those resources are through chemical processing and includes steps of calcination, leaching, precipitation, and purification. The environmental and economic sustainability of conventional Li processing has recently received increased scrutiny. Routes such as direct Li⁺ extraction may provide advantages relative to conventional Li⁺ extraction technologies, and one possible route to direct Li⁺ extraction includes leveraging intercalation materials. Intercalation material processing has recently demonstrated high selectivity towards Li⁺ as opposed to other cations. Reviews and reports of direct Li⁺ extraction with intercalation materials are limited, even as this technology has started to show promise in smaller‐scale demonstrations. This paper will review selective Li⁺ extraction via intercalation materials, including both electrochemical and chemical methods to drive Li⁺ in and out, and efforts to characterize the Li⁺ insertion/deinsertion processes.
... Xu et al., 2020, and electrochemical-battery technologies (Sun et al., 2020;Zhang et al., 2021). The diverse extraction processes of lithium from minerals and brines have been reviewed by Choubey et al (Choubey et al., 2016). ...
... However, the global recycling rate for LIBs is still less than 5% [59]. To tackle this problem and reduce the world's reliance on virgin materials, the CE approach suggests two strategies: recycling LIBs to recover raw materials such as lithium, cobalt, and manganese and re-using LIBs in stationary energy systems or other applications [60,61]. ...
A Life Cycle Assessment (LCA) quantifies the environmental impacts during the life of a product from cradle to grave. It evaluates energy use, material flow, and emissions at each stage of life. This report addresses the challenges and potential solutions related to the surge in electric vehicle (EV) batteries in the United States amidst the EV market’s exponential growth. It focuses on the environmental and economic implications of disposal as well as the recycling of lithium-ion batteries (LIBs). With millions of EVs sold in the past decade, this research highlights the necessity of efficient recycling methods to mitigate environmental damage from battery production and disposal. Utilizing a Life Cycle Assessment (LCA) and Life Cycle Cost Assessment (LCCA), this research compares emissions and costs between new and recycled batteries by employing software tools such as SimaPro V7 and GREET V2. The findings indicate that recycling batteries produces a significantly lower environmental impact than manufacturing new units from new materials and is economically viable as well. This research also emphasizes the importance of preparing for the upcoming influx of used EV batteries and provides suggestions for future research to optimize the disposal and recycling of EV batteries.
... Globally, the recycling rate of LIBs remains very low, with less than 5% of LIBs being recycled, leading to significant environmental pollution and increased reliance on virgin raw materials [82,83]. To address these challenges, the CE model proposes two main strategies: recycling to recover valuable metals, such as lithium, cobalt, and manganese, and repurposing LIBs for second-life applications in stationary energy storage systems or other applications [84,85]. ...
This article focuses on the reuse and recycling of end-of-life (EOL) lithium-ion batteries (LIB) in the USA in the context of the rapidly growing electric vehicle (EV) market. Due to the recent increase in the enactment of both current and pending regulations concerning EV battery recycling, this work focuses on the recycling aspect for lithium-ion batteries rather than emphasizing the reuse of EOL batteries (although these practices have value and utility). A comparative analysis of various recycling methods is presented, including hydrometallurgy, pyrometallurgy, direct recycling, and froth flotation. The efficiency and commercial viability of these individual methods are highlighted. This article also emphasizes the practices and capabilities of leading companies, noting their current superior annual processing capacities. The transportation complexities of lithium-ion batteries are also discussed, noting that they are classified as hazardous materials and that stringent safety standards are needed for their handling. The study underscores the importance of recycling in mitigating environmental risks associated with EOL of LIBs and facilitates comparisons among the diverse recycling processes and capacities among key players in the industry.
... Yet, this is not practical on an industrial scale as precipitation requires Li + in solution to reach super saturation. In the case of Li-containing brines, it undergoes continuous solar evaporation until Li + content reaches 60-70 g/L before purification [20]. New approaches under the concept of Direct Lithium Extraction (DLE) are in development to recover Li + from aqueous solution, such as membrane nanofiltration, electrochemical extraction, solvent extraction, aluminium/manganese/titanium-based lithium ion sieves, and ion exchange [21][22][23][24][25][26][27]. ...
... Currently, the proposed lithium extraction strategies suffer from intensive downstream purification processes, high costs, and/or high energy requirements that do not justify their adoption over the sulphuric acid process (Alhadad et al., 2023;Grasso et al., 2022). For further details on extraction techniques, readers are referred to several recent reviews: (Choubey et al., 2016;Fosu et al., 2020;Karrech et al., 2020;Li et al., 2019;Salakjani et al., 2021;Yelatontsev & Mukhachev, 2021). ...
... Global lithium resources are mainly hosted in hard rock and salt lake brine, of which salt lake-type lithium ore reserves account for more than 70%. Lithium extraction from salt lake brine is the main way to obtain and the development direction in the future (Choubey et al. 2016;Zhang et al. 2020). China is a country with large lithium resources, and lithium salt lakes are mainly concentrated in the Qinghai-Tibet Plateau, showing obvious zoning features (Han et al. 2021). ...
In recent years, the rapid development of new energy vehicles and energy storage technology, driven by the new energy industry, has led to rapid growth in lithium consumption. China has abundant lithium resources, especially in salt lake brine. Zabuye salt lake is the only salt lake in Tibet that has achieved the industrial development of lithium carbonate by using the lithium extraction technique with salinity-gradient solar pond (SGSP) so far. In this paper, the stereo-crystallization process is innovated and optimized based on an enhanced SGSP with nucleation matrix. The optimal processing parameters such as the structure design of the nucleation matrix, the spatial range of underutilized heterogeneous nucleation zone (UHNZ), and the appropriate area ratio of crystallization units have been obtained by experiments. The results show that the UHNZ should be about 0.80–2.00 m from the bottom of the pond, when the total depth of water body in the solar pond is controlled within 2.80–3.30 m and the thickness of the freshwater layer is between 0.30 and 0.60 m. For the best precipitation effect of lithium carbonate, it is suggested that the height of lower nucleation matrix (LNM) in the crystallization unit should be controlled above the height of about 0.80 m from the bottom of the pond, and the area ratio of crystallization units should be about 10%, when implementing the stereo-crystallization process. In 2022, the stereo-crystallization process with the enhanced SGSP has been fully promoted and implemented in Zabuye mining area of Tibet, increasing the output and grade of lithium concentrates significantly.
... Lithium is the lightest metal element in nature, which is widely used in daily life, aviation, medicine, the chemical industry, high-energy batteries and thermonuclear reactions, and is known as an "energy metal to promote world progress" [1,2]. With the popularity of electric vehicles, the global demand for lithium is increasing [3][4][5][6], and traditional lithium resources [7][8][9] are far from meeting market demand [10]; therefore, it is urgent to find new unconventional lithium resource supply channels. ...
The present study focuses on the synthesis of a manganese dioxide lithium ion sieve and its application for the extraction of lithium from coal fly ash. The preparation and adsorption experiments of the manganese dioxide lithium ion sieve were carried out using the orthogonal method, while the HCl elution experiment was carried out using the single factor method. The results showed that the optimum preparation conditions under which the average lithium adsorption efficiency reached 99.98% were a 10:1 mass ratio of manganese dioxide to lithium hydroxide, calcination at 800 °C for 60 min, 1.5 mol/L HCl, soaking for 24 h and stirring for 18 h. Additionally, the optimum adsorption efficiency was observed with an adsorption time of 30 min, KOH pH of 8 and KOH scrubbing time of 10 min, resulting in 100% lithium adsorption efficiency. The optimum elution conditions for lithium were determined to be an HCl concentration of 0.01 mol/L and an elution time of 40 min, giving 100% lithium elution efficiency.
... The exceptional theoretical specific capacity (3860 mAh g -1 ), low weight (6.94 g mol -1 ) and lowest redox potential (-3.04 V versus standard hydrogen electrode) of lithium metal have made it the most attractive material for battery anodes [1][2][3][4]. The presence of these characteristics makes lithium and its compounds interesting in a variety of industries. ...
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.
... In many properties, the chemistry of lithium turns out to be closer to that of magnesium (diagonal rule). The polarizing ability of Li + , which is the highest among alkali ions, leads to unusually high solvation and the formation of a covalent bond Choubey et al., 2016;Tadesse et al., 2019). Li is the only one of the alkali metals that gives a stable nitride, Li3N (like Mg). ...
The visual-polythermal approach was used to investigate the solubility of the LiNO3-NH4Cl-H2O nitrate system's constituents over a wide range of temperatures and concentrations. Internal incisions were used to study the system, and as a result, the system's polythermal solubility diagram was produced. The phase diagram delimits the crystallization fields of ice, LiNO3·2H2O, LiNO3, NH4Cl, and the new phase LiCl·3H2O, NH4NO3. The formation of a new compound was confirmed by the methods of chemical and physicochemical analysis. This system's features and composition are shown. It can provide a scientific foundation for the extraction of lithium compounds from water sources based on the knowledge learned about the solubility of the components in the system under study.
... Lithium, as the most indispensable energy storage metal, has reached a strategic level and become the real white oil in the background of global carbon neutrality. The world is rich in lithium resources, and salt lake brine and spodumene account for over 70% of the total resource reserves (Meng et al., 2021;Pankaj et al., 2016). However, with breakthrough lithium extraction technology and production process progress, lepidolite has become another important lithium source, and its strategic value is increasing yearly. ...
Surface tension measurements and molecular dynamics (MD) simulations were used to explore the flotation foam properties and self-aggregation behaviors of dodecylamine (DDA)/octanol (OCT) mixtures formed with different mole ratios at the air/liquid interface. Based on the surface and thermodynamic parameters, the DDA/OCT mixtures exhibited greater interfacial activities and adsorption capacities than their individual components. The MD simulations showed that DDA and OCT were aggregated through hydrogen bonding, coulombic forces and hydrophobic association. OCT was inserted into the DDA adsorption layer, causing the alkyl chains of both DDA and OCT to extend from water to air at varying heights and angles. The addition of OCT improved the hydration of the amino groups and reduced the overall number of hydrogen bonds. The stability of the flotation foam decreased, and the high viscosity and difficult defoaming of the DDA flotation foam were significantly improved. When the DDA/OCT mole ratio was 2:1, the included angle formed between the alkyl chains and the interface was maximized, leading to enhanced compatibility among the alkyl chains, and the hydrogen bond energy was relatively large, which showed a strong synergistic effect. The MD simulation findings were consistent with the results obtained from the lepidolite flotation and surface tension experiments conducted in this study; our results could provide a theoretical foundation for the selection of superior mixed collectors and frothers.
... It is represented in high technologies covering many areas of human activity. Lithium has become extremely important in the production of rechargeable lithium-ion batteries (LIBs), which have revolutionized the market supply and demand of renewable energy due to their unique technical characteristics (specific energy density 100-265 Wh/kg, specific power 250-340 Wh/kg, service life 400-1200 cycles) [1,2]. LIBs are used in smartphones, computers, hybrid cars, and electric vehicles. ...
The article presents the research results for the synthesis of inorganic sorbents based on manganese oxide compounds. It shows the results of the lithium sorption from brines with the use of synthesized sorbents. The effect of temperature, the molar ratio of Li/Mn, and the duration for obtaining a lithium-manganese precursor and its acid treatment was studied. The sorption characteristics of the synthesized sorbents were studied. The effect of the ratio of the sorbent mass to the brine volume and the duration of the process on the sorption of lithium from brine were studied. In this case, the sorbent recovery of lithium was ~86%. A kinetic model of the lithium sorption from brine on a synthesized sorbent was determined. The kinetics of the lithium sorption was described by a pseudo-second-order model, which implies limiting the speed of the process due to a chemical reaction.
... Measuring the lithium concentration in different silicate ores and silicate minerals is critical for evaluating the economical viability of industrial lithium extraction projects [4,5,30]. Routine analysis of lithium remains an area of active development. ...
We developed new methodologies for the quantitative determination of lithium in lithium-bearing silicate minerals and clays. This research describes direct analysis of Li in powder using an atomic-emission complex for spectrum analysis "PGS-DDP-BAES" and sintering as a sample preparation technique followed by ICP-OES analysis. A new atomic-emission complex for spectrum analysis could be used to efficiently overcome the complex matrix effects, and thus allows for the direct quantitative determination of lithium in solid samples (ores, clays). The relative standard deviation is up to 7.0%. For the extraction of Li from silicate ores and clays by sintering various parameters including sintering temperature, reaction time and additives were studied. The results indicate that the optimal temperature for sintering with NH4Cl and CaCO3 is at around 900°C. Optimum conditions for lithium extraction were found to be 300°C (30 min) and 900°C (60 min), at mass ratios of an ore : NH4Cl : CaCO3 of 1:1:8. In these conditions a lithium extraction degree of 92% is reached. Relative standard deviations for the method with sintering and ICP-OES analysis vary in the interval from 1.7 to 2.2%.
... Lithium has considerable applications in rechargeable batteries for mobile phones, laptops, electric vehicles, and extra, attending to its low density (0.53 g/cm 3 ) and negative redox potential (− 3.04 V) [1][2][3]. In addition, this element is widely used in heat transfer industries, making glasses and ceramics for special uses, producing lubricant greases, and as a flux for welding or soldering. ...
In this study, the separations of the soluble equal concentrations of high concentrate ions in seawaters and lithium ions are investigated, numerically. At the outlet of the S-, SS-, and SSS-shaped channels, the solution is lithium concentrated, by removing other ions. Electromagnetic force is used for this separation procedure. For this simulation, a numerical model of this process has been developed based on the finite volume method, computational fluid dynamics, and Lagrangian trajectories tracking method. For optimization of operational parameters including the electromagnetic field intensity and inlet fluid velocity, the genetic algorithm approach has been used in a homemade code in MATLAB software. It is observed that these channels enter different force directions on these ions and provide a balance between the electric and magnetic forces to control their movement. It is obtained that all of the impurities are removed in an optimum condition of a triple S-shaped electromagnetic channel, except potassium ions, and the percentage of lithium ions is increased from 20% at the inlet to 55% at the outlet, in an acceptable pressure drop of the passing fluid flow.
... Therefore, the direct extraction of lithium from high-Mg/Li-ratio brine is challenging, and a large amount of magnesium resources will be wasted in the extraction process [10,11]. At present, the main methods for lithium extraction from brine include precipitation, solvent extraction, adsorption and membrane methods [12][13][14]. ...
Lithium, as a green energy metal used to promote world development, is an important raw material for lithium-ion, lithium–air, and lithium–sulfur batteries. It is challenging to directly extract lithium resources from brine with a high Mg/Li mass ratio. The microstructure study of salt solutions provides an important theoretical basis for the separation of lithium and magnesium. The changes in the hydrogen bond network structure and ion association of the Li2SO4 aqueous solution and Li2SO4-MgSO4-H2O mixed aqueous solution were studied by Raman spectroscopy. The SO42− fully symmetric stretching vibration peak at 940~1020 cm−1 and the O-H stretching vibration peak at 2800~3800 cm−1 of the Li2SO4 aqueous solution at room temperature were studied by Raman spectroscopy and excess spectroscopy. According to the peak of the O-H stretching vibration spectrum, with an increase in the mass fraction of the Li2SO4 solution, the proportion of DAA-type and DDAA-type hydrogen bonds at low wavenumbers decreases gradually, while the proportion of DA-type hydrogen bonds at 3300 cm−1 increases. When the mass fraction is greater than 6.00%, this proportion increases sharply. Although the spectra of hydrated water molecules and bulk water molecules are different, the spectra of the two water molecules seriously overlap. The spectrum of the anion hydration shell in a solution can be extracted via spectrum division. By analyzing the spectra of these hydration shells, the interaction between the solute and water molecules, the structure of the hydration shell and the number of water molecules are obtained. For the same ionic strength solution, different cationic salts have different hydration numbers of anions, indicating that there is a strong interaction between ions in a strong electrolytic solution, which will lead to ion aggregation and the formation of ion pairs. When the concentration of salt solution increases, the hydration number decreases rapidly, indicating that the degree of ion aggregation increases with increasing concentration.
... Spodumene ore is calcined at 1200 • C to enhance its reactivity by converting α to β-spodumene, which subsequently passes through the sulfation process because of the higher stability of lithium sulfate in water [4,13,14]. Although lithium slag contains higher silica and alumina content, it is deficient in reactive alumino-silicate phases that might be due to the transformation of aluminosilicate into crystalline polymorphs by calcination [10]. ...
This study extensively investigates the formation of aluminosilicate gel in binary blends of lithium slag geopolymer (LSG) containing fly ash and silica fume. A comprehensive analysis of the aluminosilicate gel was performed at the micro-nano scale, employing techniques such as mineralogical, crystallographic, micromorphological, and micromechanical analysis. C-(N)-A-S-H and N-(C)-A-S-H gels were found between Si/Al ratios of 2.41–3.04 and 3.88 to 4.33, respectively. Fly ash incorporated LSG at 45% alkaline activator yielded the highest average nano-indented modulus of 22.54 GPa. Statistical Gaussian deconvolution was employed to categorize mineral phases in nano-indentation of LSG, revealing substantial distinctions indicated by the low p-values. Carbonation in silica fume incorporated LSG was affirmed by selected area electron diffraction (SAED) patterns of calcite crystallites. The microstructure of LSG containing fly ash was stiffened by the growth of needle crystals of hydroxy-sodalite and aluminosilicate gel. Thus, the formation of C-(N)-A-S-H gel and hydroxy-sodalite governs the strength development of LSG binary blends.
In recent years, the rapid development of new energy technologies has driven swift progress in lithium exploitation. Compared to brine sources, lithium is more widely distributed in mineral deposits. Therefore, the development of efficient and clean processes for lithium extraction from ores, along with the comprehensive utilization of resources, is an inevitable trend in the development of this field. This review starts by examining the strategic significance of lithium, analyzing the primary types of lithium ores, and providing a comprehensive summary and explanation of lithium ores worldwide. The categorization of lithium ores, coupled with a discussion on the principles of various lithium ores extraction technologies, forms the basis for this review. The focus lies on summarizing the comprehensive utilization of resources during the lithium ores production process, addressing challenges within the technological processes. Additionally, exploration into the development direction of new technologies emphasizing cleanliness, efficiency, and integrated utilization is undertaken.
Lithium is a crucial component in rechargeable lithium-ion batteries for many applications, including the powering of electric vehicles and stationary energy storage systems. This investigation focused on two hybrid pseudocapacitive materials, the polystyrene sulfonate-MXene composite (PM) and the sodium titanate/graphene oxide composite (NG), for lithium ions recovery from aqueous Li+ resources. This was achieved by selectively removing unwanted divalent Ca2+ and Mg2+ ions, as well as monovalent K+ ions, through capacitive deionization (CDI) using a single-cell system, resulting in a final solution enriched with Li+ ions. Based on the ion selectivity order observed previously as Mg2+≈ Ca2+ > K+ > Li+, a series of CDI experiments were conducted with sequential steps to remove more selective ions first and to obtain a lithium-enriched solution with higher purity and maximum extracted fraction. Both PM and NG electrodes demonstrated promising performance when tested in binary, ternary, and quaternary ionic solutions with the recovered lithium solution purity in the range of 59.09 %-95.94 % and 59.75 %-77.17 %, respectively. Further, the highest enrichment factor values observed were SLi+,Mg2+; 268.1 for PM and SLi+,Ca2+; 44.25, for NG electrodes. The PSS-modified MXene composite electrode in obtaining the Li+ solution with the highest purity when separated Ca2+ from a binary solution. These findings offer valuable insights into the selective electrosorption of divalent ions over lithium ions through the utilization of ion intercalation pseudocapacitive nanocomposite electrodes. The obtained results hold significance in advancing novel non-precipitation techniques for the recovery of lithium ions from aqueous lithium resources.
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.
Demand for lithium‐ion batteries for use in electric vehicles is driving lithium demand. A large increase in demand between now and 2040 is expected due to increasing electrification of the transport and energy sectors of the economy. This is in part due to an interest in improving air quality in cities and in the reduction of greenhouse gas emissions when electricity is generated without fossil fuel combustion. Currently, the two major natural sources of lithium for use in lithium‐ion batteries are brines and hard‐rock minerals. Lithium‐bearing clays have also been investigated as a potential source of lithium. Battery recycling is another potential source. Lithium in hard‐rock minerals is predominantly found in pegmatites. Lithium‐bearing minerals that may occur in pegmatites include petalite, lepidolite, and spodumene. The latter is currently the predominant hard‐rock lithium source. Following comminution, a number of treatments or combinations of treatments can be used to produce materials suitable for the final stage of purification of lithium products. Most involve high‐ or very‐high‐temperature treatments with various reagents followed by water leaching, although a few treat lithium‐bearing feed directly with acid leaching. Other elements are co‐leached and must be separated from lithium to allow the production of high‐purity lithium carbonate or lithium hydroxide, which are then used to manufacture lithium‐ion battery cathodes.
Spodumene flotation stands as the most commonly used method to concentrate lithium minerals. However, it faces significant challenges related to low collector recoveries and similarity in the surface characteristics of the minerals, which make the effective separation of this valuable mineral difficult. For this reason, numerous researchers have conducted studies to address and confront this problem. In this work, an exhaustive bibliographic search was carried out using keywords and search queries, and the results were structured in three sections according to temporal, methodological, and thematic criteria. The first section covers the period from 1950 to 2004, focusing on experimental tests. The second section covers from 2004 to the present and focuses on flotation tests and measurement analysis. Simultaneously, the third section spans from 2011 to the present and is based on molecular dynamics simulations. Topics covered include spodumene surface properties, the influence of metal ions, pre-treatment techniques, and the use of collectors. Ultimately, molecular dynamics simulations are positioned as a tool that accurately represents experimental phenomena. In this context, specialized software such as Materials Studio or Gromacs prove to be reliable instruments that allow a detailed study of mineral surfaces and other elements to be carried out, which justifies their consideration for future research in this scientific field.
El litio desempeña un papel fundamental en el desarrollo de aplicaciones tecnológicas, por lo que ha sido denominado un “elemento crítico de energía”. Este hecho requiere del aprovechamiento integral de los recursos de litio disponibles, tales como salares, minerales y residuos electrónicos.
El espodumeno es el mineral más importante para la extracción de litio a nivel mundial. Argentina posee sus principales reservas ubicadas en Salta, Catamarca, San Luis y Córdoba. Industrialmente, el mineral debe calcinarse a 1100°C y, luego, digerirse con H2SO4 concentrado a 250°C para extraer el litio, generando un elevado consumo energético, subproductos no comercializables, pasivos ambientales y sólo un aprovechamiento 5% del mineral. En este marco, resulta fundamental y de gran interés desarrollar nuevas metodologías extractivas de litio a partir de minerales.
Esta tesis doctoral presenta el desarrollo de un nuevo proceso de extracción de litio a partir α-espodumeno empleando bifluoruro de amonio fundido, seguido por la recuperación de silicio y aluminio por vías hidrometalúrgicas. Este estudio comprende:
-El análisis termocinético del agente fluorante, las vías de reacción de la fluoración del mineral en función de la temperatura y el comportamiento térmico de los subproductos.
-La optimización de los parámetros operativos del proceso térmico de fluoración y, luego, de la disolución de los productos de litio y aluminio.
-El estudio de parámetros operativos de la síntesis de sílice amorfa como subproducto de silicio, y el proceso de recuperación de criolita como subproducto de aluminio.
El proceso desarrollado mostró una alta efectividad, alcanzando extracciones de litio de hasta 97% a temperaturas de ~165°C, muy inferiores a las empleadas por otros métodos pirometalúrgicos. Además, se lograron recuperaciones de silicio y aluminio del 91 y 94% como sílice amorfa y criolita, respectivamente. De esta manera, además de la extracción de litio, se obtuvieron subproductos de aplicación industrial, dando un mayor aprovechamiento de todos los componentes del mineral.
Selective electrodialysis (ED) is a promising membrane-based process to separate Li⁺ from Mg²⁺, which is the most critical step for Li extraction from brine lakes. This study theoretically compares the ED-based Li/Mg separation performance of different monovalent selective cation exchange membranes (CEMs) and nanofiltration (NF) membranes at the coupon scale using a unified mass transport model, i.e., a solution-friction model. We demonstrated that monovalent selective CEMs with a dense surface thin film like a polyamide film are more effective in enhancing the Li/Mg separation performance than those with a loose but highly charged thin film. Polyamide film-coated CEMs when used in ED have a performance similar to that of polyamide-based NF membranes when used in NF. NF membranes, when expected to replace monovalent selective CEMs in ED for Li/Mg separation, will require a thin support layer with low tortuosity and high porosity to reduce the internal concentration polarization. The coupon-scale performance analysis and comparison provide new insights into the design of composite membranes used for ED-based selective ion–ion separation.
Multi-channel exploitation and utilization of lithium-bearing resources may be the future sustainable development trend of the lithium industry. Lithium-rich bauxite flotation tailings are a potential lithium resource. This study proposed a green and effective lithium extraction process employing sodium bicarbonate solutions to leach lithium-rich bauxite flotation tailings. 91.75% of lithium could be leached over a time of 60 min using a 300 g/L sodium bicarbonate solution at 280 °C with a liquid–solid ratio of 10. Notably, potassium’s leaching efficiency was lower than lithium’s, whereas other elements, such as aluminum and silicon, were difficult to leach. Furthermore, the experimental results verify the results of the thermodynamic analysis. The leaching mechanism of lithium and potassium in sodium bicarbonate solution is that sodium ions in the sodium bicarbonate solution substituted Li+ of cookeite and K+ of illite, respectively. Thus, this research could provide a new way to efficiently and economically utilize clay-rich lithium resources.
The mechanism of leaching lithium and potassium from tailings was considered to involve the ion-substitution reaction. Sodium ion in the sodium bicarbonate solution substituted Li+ of cookeite and K+ of illite, respectively.
Extracting lithium from spodumene by sulfuric acid roasting is the largest commercialized way at present, which not only consumes a large amount of energy but also produces massive waste residue that will cause environmental problems. In this work, a new process for extracting lithium by directly decomposing α‐spodumene through alkali calcination is designed. The reaction of α‐spodumene with Na2CO3 at 750 °C for 2 h can decompose it and form nepheline and lithium silicate/sodium silicate. The nepheline and soluble lithium silicate/sodium silicate are separated by water leaching, and 93.9 % of lithium can be leached under optimal conditions. In addition, the synthesis of nano‐kaolinite is investigated with nitric acid solutions. Conversions of 98.7 % were obtained with 0.4 M nitric acid at 250 °C and an L/S ratio of 17.5 L/kg. The water leachate can precipitate Li2CO3 with a purity of 99.0 % by CO2 after desilicated by CaO. The final yields of Li2CO3 and kaolinite relative to the Li and Si content of the starting minerals are 91.4 % and 48.5 %, respectively. This new method achieves the full utilization of spodumene with lower energy consumption and demonstrates great potential for industrial applications.
Lithium isotope measurement in spodumene by femtosecond LA‐MC‐ICP‐MS was investigated and the influence of plasma operating conditions and data reduction strategy on accuracy and precision was studied. It was found that “hot” plasma conditions led to an unstable baseline signal and substantial variations in the Li isotope ratios. By adding a constant amount of water to the carrier gas, a stable baseline was achieved and isotope ratios became reproducible and were consistent with data from solution‐based MC‐ICP‐MS. The resulting biases were within ± 0.51‰ and the reproducibility was better than 0.09‰. Comparison of Li isotope ratios resulting from different data evaluation schemes showed that the mean of the transient intensity ratios, integration of the entire or a user‐defined period of the ion signals resulted in good agreement with solution‐based data, while linear regression underestimated the Li isotope ratios. It was also found that “cool” plasma operation produced a stable baseline signal, but the Li isotope results were biased by up to ‐4.3%, irrespective of water introduction and the data evaluation scheme. With the optimised “hot‐wet” conditions, the Li isotope ratios in eleven spodumene materials were determined which successfully allowed distinguishing regional deposits and partially veins of the available samples.
The recovery of lithium as lithium aluminate from Egyptian bitterns was investigated. Studies were performed on synthetic Li + solution and on three high – salinity end brines which contain Li + of concentrations varying between 5.5-19.5 ppm. Pretreatment with a mixture of Na 2 SO 4 -Na 2 CO 3 is achieved to precipitate BaSO 4 , SrCO 3 , CaCO 3 and possibly MgCO 3 . A co-precipitation method was employed using aluminum salt as (AlCl 3 .6H 2 O). Lithium ion is adsorbed onto aluminum hydroxide, which is freshly produced by adding AlCl 3 .6H 2 O and Na OH to the brines at Al 3+ / Li + molar ratio≈ 5-7. Results obtained indicate that high Li+ adsorption was performed at pH = 6-7 for Alexandria-Arish and Emissal salines, even for small concentration of aluminum salt added. Also, Lithium ions uptake decreased with increasing adsorption temperature from 10ºC to 30ºC but over 30ºC increase in temperature does not affect lithium uptake on Al(OH) 3 , which proved that the process is physical adsorption. Equilibrium isotherms have been determined for the adsorption of Li + onto Al (OH) 3 at 30ºC and pH= values (5 to 9), the maximum adsorption capacity of Al(OH) 3 at 30ºC and pH = 9 is 123 mg/gm. The results indicated that applied isotherms were shown to be "favorable" and were fitted with Langmuir and Freundlich isotherms. Li + desorption from Al(OH) 3 was investigated using hydrofluoric acid (HF) or sulphuric acid (H 2 SO 4) with different concentrations, and results obtained showed that HF is more efficient than H 2 SO 4 concerning Li + desorption. From the obtained results, Li ion can be recovered successfully from bittern and saline solutions. [Journal of American Science. 2010;6(11):301-309]. (ISSN: 1545-1003).
This paper critically assesses if accessible lithium resources are sufficient for expanded demand due to lithium battery electric vehicles. The ultimately recoverable resources (URR) of lithium globally were estimated at between 19.3 (Case 1) and 55.0 (Case 3) Mt Li; Best Estimate (BE) was 23.6 Mt Li. The Mohr 2010 model was modified to project lithium supply. The Case 1 URR scenario indicates sufficient lithium for a 77% maximum penetration of lithium battery electric vehicles in 2080 whereas supply is adequate to beyond 2200 in the Case 3 URR scenario. Global lithium demand approached a maximum of 857 kt Li/y, with a 100% penetration of lithium vehicles, 3.5 people per car and 10 billion population.
Magnesium-doped lithium manganese oxides LimMgxMnIIIyMnIVzO4 (0 < x ¯ 0.5) with cubic spinel structure were synthesized by a coprecipitation method followed by calcination at 450 °C in air. Protonated samples were obtained after treatment with HCl solution. Chemical stability is very important for lithium uptake in industry. We used 0.5M HCl for desorption of lithium, then dissolution of Mn decreased from 5.8 wt% for a sample without Mg to 1.0 wt% for a Mg-doped sample (Mg/Mn = 0.33). Raw brine was collected from the Salars de Uyuni, Bolivia. The effects of magnesium-doping on lithium adsorptive properties of the protonated samples in NaHCO3 containing brine were studied by a batch method. The results showed that lithium adsorptive capacity and chemical stability of the protonated samples increased with increase in Mg/Mn ratio. The regeneration of the sample with Mg/Mn = 0.33 up to 10 cycles showed good performance with lithium adsorptive capacity of 23-25 mg/g at pH 6.6, and the dissolution of manganese ca. 0.25 wt% Mn.
The aim of the present work is to study the separation of lithium from salt lake brines by NF and LPRO. NF90 membrane compared to the XLE a LPRO membrane appeared more efficient for Li+ extraction due to its higher hydraulic permeability to pure water and 0.1 M NaCl solution, its lower critical pressure (Pc = 0), its higher selectivity between monovalent ions (40%) obtained at low operating transmembrane pressure (below 15 bar) and its lower average roughness (105 ± 10 nm) decreasing the propensity to be fouled. NF90 exhibited 100% rejection of magnesium in the first step separation from brine diluted ten times as 15% for Li+, with a final separation of 85% between Mg2 +/Li+. The permeability to the diluted brine is 0.7 L.h− 1.m− 2.bar− 1 usable to size full scale experiments, but the fouling mechanism has to be discovered in the future work. In a second step we have not succeeded to separate totally Li+ and Na+ in the permeate obtained before (15% of separation only between Li+ and Na+). To solve this problem, we did dialysis. We obtained a total separation between Li+ and Na+ with a diffusion flux (4.42 10− 7 mol.s− 1.m− 2 at 20 °C) for NaCl 0.1 M 5 times higher for NF90 vs XLE.
The granites of South-West England are a potential source of lithium which is generally found within the mica mineral, zinnwaldite. It is mainly found in the central and western end of the St. Austell granite. When kaolin extraction occurs in these areas a mica-rich waste product is produced which is currently disposed of in tailings storage facilities. In this study a tailings sample containing 0.84% Li2O was upgraded by a combination of froth flotation, using dodecylamine as the collector, and wet high intensity magnetic separation (WHIMS) to 2.07% Li2O. The concentrate was then roasted with various additives, including limestone, gypsum and sodium sulphate, over a range of temperatures. The resulting products were then pulverised before being leached with water at 85°C. Analysis of these products by XRD revealed that the water-soluble sulphates, KLiSO4 and Li2KNa(SO4)2, were produced under specific conditions. A maximum lithium extraction of approximately 84% was obtained using gypsum at 1050°C. Sodium sulphate produced a superior lithium extraction of up to 97% at 850°C. In all cases iron extraction was very low.Preliminary tests on the leach solution obtained by using sodium sulphate as an additive have shown that a Li2CO3 product with a purity of >90% could be produced by precipitation with sodium carbonate although more work is required to reach the industrial target of >99%.
An ore sample from a pegmatite deposit at Wekusko Lake in northern Manitoba contained 1.70% lithium oxide, Li 2O. Scanning electron microscope analysis showed that lithium is present as spodumene at a concentration of approximately 7.4% Li 2O. The SEM micro-analysis identified that the Fe 2O 3 concentration ranges between 0.94 and 1.64%. It was further found that potassium and sodium oxide concentrations in the spodumene are relatively low, 0.01% K 2O and 0.21% Na 2O. Major minerals associated with the spodumene are Na-feldspar, K-feldspar, and quartzite. Muscovite, apatite, and garnet are present at low concentrations. Despite its relatively high iron content, it is expected that this spodumene is suitable for the glass and chemical industry. The extraction process of lithium as Li 2CO 3 from the ore consists of oleic acid froth flotation resulting in a concentrate containing around 6.6% Li 2O. A heat treatment at 1100 °C of the concentrate is subsequently applied in order to produce a chemically activated spodumene. Subsequently, the spodumene is subjected to sulphuric acid roasting, leaching, solution purification and precipitation of Li 2CO 3, containing above 98% Li 2CO 3.
Gypsum and limestone methods commonly used to treat lepidolite ores, were examined in this study to process lithium bearing wastes, which originated from gravity dressing of Sn-W ores mined in the past in the Czech Republic. These wastes, which contain on average 0.20% Li in the form of polylithionit (K[AlFeLi][Si3Al]O10OH)F) - a variety of zinnwaldite, and about 0.30% Rb were subjected to dry magnetic and grain size separations to obtain a zinnwaldite concetrate with 1.37% Li and 1.70% Rb. It was found that processing of the zinnwaldite concentrate by gypsum method makes it possible to extract almost 90% Li into aqueous liquors as Li2SO4. At the same time, it is possible to extract only 80% lithium from the identical zinnwaldite concentrate as LiOH, using limestone method. However, application of limestone method to processing zinnwaldite concentrates will be more advantageous compared with the gypsum method if zinnwaldite concentrates will be utilized for both lithium and rubidium production.
This book is concerned with two major industrial minerals: Lithium and Calcium Chloride. The geology of their deposits is first reviewed, along with discussions of most of the major deposits and theories of their origin. The commercial mining and processing plants are next described, followed by a review of the rather extensive literature on other proposed processing methods. The more important uses for lithium and calcium chloride are next covered, along with their environmental considerations. This is followed by a brief review of the production statistics for each industry, and some of their compounds phase data and physical properties. • Describes the chemistry, chemical engineering, geology and mineral processing aspects of lithium and calcium chloride • Collects in one source the most important information concerning these two industrial minerals • Presents new concepts and more comprehensive theories on their origin.
The construction and operational experience of solar pond in Zabuye Saline Lake were introduced in the paper. The salinity gradient in the about 3588m2 pond was experimentally determined. The suitable method for establishing the salinity gradient and temperature gradient were developed. The experimental results show that the method introduced in this work can save large amount of fresh water in building the temperature and salinity gradient in the solar pond. The control technologies in the solar pond operation was determined based our experimental results and used in real operation.
The extraction kinetics of lithium with a mixture of a β-diketone and a neutral organophosphorus compound was studied using a hollow fiber membrane extractor in order to obtain fundamental information to elucidate the extraction mechanism and to develop a recovery process for lithium. We found that the hydrophobicity of neutral organophosphorus compounds affects the extraction kinetics of lithium with a mixture of a β-diketone and a neutral organophosphorus compound. The experimental results are explained by the film theory with interfacial reaction in which the rate-determining step is the formation and desorption of the lithium complex at the heptane-water interface. This mechanism of lithium extraction with a mixture of a β-diketone and a neutral organophosphorus compound is also based on the experimental results of the interfacial adsorption equilibrium of the extractants. The molecular dynamics (MD) simulation at the heptane-water interface suggested that the extraction kinetics of lithium with a mixture of a β-diketone and a neutral organophosphorus compound is affected by the adsorbed state of the lithium complex at the interface where the rate-determining step of the interfacial reaction took place.
A zinnwaldite concentrate with 1.40% Li processed in this study was prepared from zinnwaldite wastes (0.21% Li) using dry magnetic and grain size separations. Zinnwaldite wastes originated from dressing Sn-W ores, which were mined in the past in the Czech Republic in Cínovec area. The extraction process of lithium, so-called gypsum method consisted of sintering the concentrate with CaSO4 and Ca(OH)2, subsequent leaching of the sinters obtained in H2O, solution purification and precipitation of Li2CO3. It was observed that almost 96% lithium extraction was achieved if sinters prepared at 950°C were leached at 90°C, liquid-to-solid ratio = 10: 1, reaction time of 10 min. The weight ratio of the concentrate to CaSO4 to Ca(OH)2 was 6 : 4.2 : 2. Lithium carbonate product containing almost 99% Li2CO3 was separated from the condensed leach liquor, from which calcium was removed by carbonate precipitation.
Spodumene is one of the principal sources of Li and the most important Li mineral in pegmatites. Experiments have been carried out at 450°C and 600°C at 4 kbar and 750°C at 1.5 kbar to study the equilibrium between spodumene, albite, quartz, and the co-existing hydrothermal chloride solution. Solid-solution formation in spodumene as well as in albite is very much restricted. When spodumene coexists with albite and quartz, the alkali composition of the fluid is buffered. The value of the ratio Na/(Na + Li) of the fluid has been determined to be 0.550 ± 0.020 at 450°C, and 0.485 ± 0.025 at 600°C, conditions at which the stable form of spodumene is α spodumene. At 750°C, 1.5 kbar, the stable form is the high-temperature polymorph β spodumene. In the presence of an excess of quartz, the assemblage albite + β spodumene partially melts from Ab30-Sp70 to An75-Sp25. The value of the ratio Na/(Na + Li) in the fluid buffered by coexisting albite and spodumene, with or without melt, is constant and has been determined to be 0.510 ± 0.020 at 750°C. -Authors
Containing 10.2 Mt Li, Salar de Uyuni is known to be the richest resource of Li in the world. A high Mg/Li mass ratio of 21.2:1 of the Uyuni salar brine used in this study is a significant factor hindering the effective lithium recovery. Stabcal modelling was first conducted to study the conditions and chemical speciation of various species involved in the selective precipitation of Mg and Ca oxalate. Along with the addition of oxalic acid, the effect of pH was then studied in order to determine optimal conditions to selectively remove Ca and achieve high Mg yield subsequently. At an Oxalate/Ca molar ratio of 6.82:1 and pH < 1, ~ 80% of Ca could be removed from brine without co-precipitation of Mg oxalate. A NaOH/Mg/Oxalate molar ratios of 1.95:1:1 to 3.21:1:1.62 in the range of pH 3-5.5 was used for the Mg precipitation. A recovery of > 95% Mg was obtained (precipitate containing mostly Mg oxalate) together with the K and Li losses of up to 35% from the original brine. Washing would remove Li, K contaminants and the co-precipitated sodium sulphate and oxalate. Their absence from the final precipitate was confirmed by XRD analysis. The high purity (99.5% grade) Mg precipitate obtained could be used as a precursor for MgO production.
Spodumene is the most important lithium containing hard rock mineral. In order to extract lithium from spodumene concentrate by leaching, the crystal structure of spodumene must be converted from the natural monoclinic α-form to the tetragonal β-form. The technical possibilities to generate the heat to the conversion process of spodumene concentrate via microwaves were studied. The heat treatment experiments were carried out with a domestic microwave furnace (700 W) with silicon carbide susceptor and with the conventional resistance heated furnace as a reference. In the microwave furnace the phase transformation of spodumene began after 110 s of heating and samples were converted almost completely to β-spodumene after 170 s. Partial melting of gangue minerals was observed in samples after 170 s of heating. Heating in microwave furnace for 170 s corresponded with the heating of approximately 480-600 s at temperature of 1100 °C in the conventional furnace. In addition to α- and β-forms an intermediate phase, hexagonal γ-spodumene, was identified from samples heated with both furnaces. The conversion of spodumene samples was verified with X-ray diffraction (XRD) and with field emission scanning electron microscope (FESEM).
The crystal structure of masutomilite from Tanakamiyama, Ohtsu, Japan, has been refined by the X-ray single crystal method. The chemical formula is (K1.79 Na0.15 Rb0.14)2.08 (Li2.54 Mn0.992+ Fe0.182+ Fe0.063+ Al1.96 Ti0.01)5.74 (Si6.65 Al1.35)8.00 O19.64 (F3.16 (OH)1.20)4.36 and the crystal data are as follows: monoclinic, C2, a = 5.262(2), b = 9.102(3), c = 10.094(3)Å, β = 100.83(2)°, Z = 1. The final R-value converged to 0.046 (wR = 0.052), using 519 independent reflections. The octahedral cation ordering, small Al and Fe3+ in the M(2) site, and the remaining large Li and Mn2+ in the M(1) and M(3) sites, results in the non-centrosymmetric C2 structure. The mean bond length of M(2)–O is 1.89Å, and those of M(1)–O and M(3)–O are 2.13 and 2.12Å, respectively.
Given their unique resources, the carbonate salt lakes in Tibet offer significant advantages in the extraction of lithium, but some disadvantages are being exposed in production. These disadvantages include the long period of lithium extraction and the low grade of lithium carbonate caused by geographical conditions and climate factors of the Qinghai–Tibet plateau. Based on the above reasons, we rebuilt the traditional solar ponds by introducing a kind of heat exchanger in a bid to speed up the temperature rise of brine, whereby we planned to make use of the high-temperature geothermal resources around the lakes to produce lithium carbonate in large-scale applications. We carried out a small lithium-extraction experiment with hot water as the heat source for the purpose of verifying the feasibility of lithium extraction by geothermal-salinity gradient solar pond (G-SGSP). In the experiment, the contrastive analysis method was employed as a means to study the relationship between ion diffusion and temperature, as well as salinity in G-SGSP and these controllable factors’ impact on the precipitation of lithium carbonate. The results of the experiment show that it is highly feasible to extract lithium through G-SGSP, thus enhancing the efficiency of lithium extraction and generating higher-grade lithium carbonate. Thus, the experiment serves as a dramatic reference for extracting lithium from Dangxiong Tso Salt Lake through the application of geothermal resources.
Chlorination roasting was used to extract lithium as lithium chloride from β-spodumene. The roasting was carried out in a fixed bed reactor using calcium chloride as chlorinating agent. The mineral was mixed with CaCl2 on a molar ratio of 1:2. Reaction temperature and time were investigated. The reactants and roasted materials were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD) and atomic absorption spectrophotometry (AAS). The mineral starts to react with CaCl2 at around 700 °C. The optimal conditions of lithium extraction were found to be 900 °C and 120 min of chlorination roasting, under which it is attained a conversion degree of 90.2%. The characterization results indicate that the major phases present in the chlorinating roasting residue are CaAl2Si2O8, SiO2, and CaSiO3.
The increased use of fossil fuel combustion to produce electricity increases carbon dioxide gas levels in the atmosphere, causing a greenhouse effect. Thus, electricity from renewable and sustainable energy resources such as solar, wind, and tide has moved to the center of attention. LIBs have been successfully used as power sources in most of today's portable electronics. Although LIBs have been optimized to meet the requirements of portable electronics, some intrinsic characteristics make the current LIBs less feasible for large-scale stationary ESSs, where the cost, safety, and long cycle life become relatively more important than energy densities. A variety of electrode materials for ARLBs have been introduced. Unlike the electrode materials used in organic electrolyte systems, the redox potentials of electrode materials in aqueous electrolytes should be within or near the electrolysis potentials of water.
In this study lithium was extracted from β-spodumene with hydrofluoric acid leaching. The operating parameters studied were: solid liquid ratio, stirring speed, particle size, temperature, reaction time and HF concentration. Reagents and products were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), atomic absorption spectroscopy (AAS), scanning electronic microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The lithium extraction efficiency of 90% could be reached with solid-liquid ratio, 1.82% (w/v); temperature, 75 °C; HF concentration, 7% (v/v); stirring speed, 330 rpm and reaction time, 20 min. Al and Si can be precipitated as Na3AlF6 and Na2SiF6 with a recovery of 92%. Lithium carbonate was separated from leach liquor by carbonatation and crystallization during water evaporation, with recovery values of 90%, approximately.
The extraction of lithium by means of the chlorination roasting of β-spodumene has been studied in the temperature range from 1000 to 1100 °C for periods of time from 0 to 180 min. The roasting was carried out in a fixed bed reactor using pure gaseous Cl2 as chlorinating agent. The reactants and products were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), atomic absorption spectrometry (AAS), scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The roasting of β-spodumene with pure Cl2 at 1100 °C for the period of 150 min led to quantitative extraction of lithium as lithium chloride. The solid products of the reaction of β-spodumene with Cl2 were found to be Al6Si2O13 (mullite), and Si2O (cristobalite).
Iron sulphate roasting and water leaching were investigated to extract lithium from lepidolite in this study. HSC modelling was used to simulate the process of roasting lepidolite with FeSO4·7H2O and CaO. Based on HSC, three-dimensional models were derived to predict the effect of temperature, SO4/Li and Ca/F molar ratios on the production of S- and F-containing gases (SO2, SO3, HF) and Li species (Li2SO4, LiKSO4) during roasting. It is believed that temperature and SO2/SO3 gases controlled the extraction of lithium from lepidolite during roasting while more soluble Li sulphate species determined the recovery of lithium during leaching. Using optimum parameters selected from HSC, roasting tests were conducted to produce calcines for leaching. Optimum roasting conditions were experimentally determined as 850 °C, 1.5 h, and SO4/Li and Ca/F molar ratios of 3:1 and 1:1, respectively. Roasting in a closed environment led to more Li extracted than with an open system. Leaching the calcines obtained from the open and closed systems with a water/calcine mass ratio of 1:1 at room temperature for 1 h yielded leach liquors containing ~ 7.9 g/L Li and ~ 8.7 g/L Li, corresponding to ~ 85% and ~ 93% extractions of Li from lepidolite, respectively.
Chlorination roasting followed by water leaching process was used to extract lithium from lepidolite. The microstructure of the lepidolite and roasted materials were characterized by X-ray diffraction (XRD). Various parameters including chlorination roasting temperature, time, type and amount of chlorinating agents were optimized. The conditional experiments indicate that the best mass ratio of lepidolite to NaCl to CaCl2 is 1:0.6:0.4 during the roasting process. The extraction of lithium reaches peak value of 92.86% at 880 °C, potassium, rubidium, and cesium 88.49%, 93.60% and 93.01%, respectively. The XRD result indicates that the major phases of the product after roasting lepidolite with mixture of chlorinating agents (CaCl2 and NaCl) are SiO2, CaF2, KCl, CaSiO3, CaAl2Si2O8, NaCl and NaAlSi3O8.
A hydrometallurgical process was developed to recover lithium from a brine collected from Salar de Uyuni, Bolivia, which contains saturated levels of Na, Cl and sulphate, low Li (0.7–0.9 g/L Li) and high Mg (15–18 g/L Mg). Unlike other commercial salar brines currently being processed, the high levels of magnesium and sulphate in Uyuni brine would create difficulties during processing if conventional techniques were used. A two-stage precipitation was therefore first adopted in the process using lime to remove Mg and sulphate as Mg(OH)2 and gypsum (CaSO4.2H2O). Boron (at 0.8 g/L in the raw brine), a valuable metal yet deleterious impurity in lithium products, could also be mostly recovered from the brine by adsorption at a pH lower than pH11.3 in this first stage. The residual Mg and Ca (including that added from lime) which were subsequently precipitated as Ca–Mg oxalate could be roasted to make dolime (CaO ∙ MgO) for re-use in the first stage of precipitation. Evaporation of the treated brine up to 30 folds would produce 20 g/L Li liquors. The salt produced during evaporation was a mixture of NaCl and KCl, containing acceptable levels of sulphate, Mg, Ca, etc. The final precipitation of lithium at 80–90 °C produced a high purity (99.55%) and well crystalline lithium carbonate.
Salt roasting with Na2SO4 + CaCl2 followed by water leaching was used to extract alkali metals from lepidolite. The experiments indicated that the best mass ratio of lepidolite /Na2SO4/CaCl2 during roasting was 1:0.5:0.3. The extraction of Li, Rb and Cs were all > 90% after 0.5 h at 880 °C. The recovery of Li was essentially constant when roasted at 830–930 °C. The flexible roasting condition is easily controlled in industrial application. After leaching in water, the solution was cooled to − 5 °C for 2 h to crystallise 92.1% of the sulphate and 3.9% of the chloride as Na2SO4·10H2O and NaCl, respectively. Evaporation and precipitation using Na2CO3 produced Li2CO3 crystals with > 99.5% purity and a solution from which Rb and Cs could be recovered.
A novel technique was developed to extract lithium from lepidolite.The lepidolite was pre-roasted at a high temperature with water steam atmosphere for defluorination. Then the defluorinated lepidolite was leached in a lime–milk autoclave. Various parameters including the defluorination percentage of lepidolite, milling time, temperature, time, lime-to-defluorinated lepidolite ratio, and liquid-to-solid ratio in the leaching process were optimized. The lithium extraction efficiency can reach 98.9% under the optimal conditions. The purity of the lithium carbonate obtained can be up to 99.9%.
Key factors controlling the extraction of lithium from a lepidolite concentrate (2.55% Li) using a two-stage process based on roasting with Na2SO4 and water leaching were determined in this study. HSC software was used to predict lepidolite decomposition characteristics and products yielded from roasting. From this simulation roasting was conducted at 850–1000 °C with different sodium sulphate additions (set at sodium sulphate-lithium molar ratios of 1:1 to 3:1) in 0.5–2 h to yield several calcines for leaching. Stabcal modelling was applied to investigate the stability of various Li species formed during water leaching. From the simulation it was identified that LiKSO4, as one of the main Li-containing products formed in the calcine, has a low solubility and therefore controls the release of Li into water during leaching. The low solubility of LiKSO4 at 25 °C indicated by Stabcal was confirmed during leaching at different water–calcine mass ratios from 5:1 to 15:1. Leaching under these conditions only yields liquors containing < 1.0 g/L Li, corresponding to Li extractions of 45–48%. The Li extraction was significantly improved at 85 °C, yielding liquors containing 1–3 g/L Li, corresponding to extractions of 47–90%, with lower extractions of Li achieved at higher Li concentrations. At best, 90.4% of lithium was extracted (at water–calcine mass ratio 15:1, 85 °C and 3 h) using calcines roasted at 1000 °C for 0.5 h (using Na2SO4 — Li molar ratio of 2:1).
Lithium and rubidium were extracted from zinnwaldite [KLiFe2 +Al(AlSi3)O10(F,OH)2] by (1) its sintering with and CaCO3 powders and (2) water leaching the obtained sinters—the alkali digestion process. The experimental results showed that sintering proceeded in three partly overlapping stages: (1) decomposition of zinnwaldite at temperature up to 800 °C, (2) formation of new phases in the temperature range between 750 and 835 °C, and (3) formation of amorphous glassy phase at temperature above 835 °C. Densification of the reaction mixture occurred via a liquid phase sintering at temperatures above 750 °C and diffusion of calcium, potassium, silicon and rubidium resulted in the formation of the new phases. The decomposition of zinnwaldite and the formation of the new phases increased extraction of lithium and rubidium. The formation of glassy phase probably hindered extraction of lithium but did not affect that of rubidium because of its outward diffusion to sinter's surface. The optimal extraction efficiencies of 84% of lithium and 91% of rubidium were achieved at sintering temperature of 825 °C and leaching temperature of 95 °C. The good fit of the hyperbolic and uniform reaction models to the leaching data indicated that dissolution of lithium and rubidium proceeded through two stages. Application of the shrinking core model showed that dissolution of lithium was controlled by diffusion. The formation of a layer of Ca(OH)2 on surface of sinters apparently slowed and then terminated dissolution of lithium and rubidium in the later stage of leaching.
Sulfation roasting followed by water leaching process was used to extract lithium from lepidolite. Various parameters including roasting temperature, the amount of additions, and solid/liquid ratio in leaching process were optimized. The lithium extraction efficiency of 91.61% could be reached with a mass ratio of lepidolite/Na2SO4/K2SO4/CaO of 1:0.5:0.1:0.1, and roasting at 850 °C for 0.5 h. XRD analysis showed that sulfation roasting caused the decompositions of the original aluminosilicate to NaSi3AlO8, KAlSi2O6 and CaAl2Si2O8. The phases of CaF2 and Ca4Si2O7F2 are observed due to the addition of CaO.
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.
In this paper, the kinetics chlorination of β-spodumene for the extraction of lithium has been studied using gaseous chlorine as chlorinating agent. The effect of chlorine flow rate, temperature, mass of the sample, and partial pressure of Cl2 was investigated. The study of the effect of chlorine flow rate indicated that the chlorination of β-spodumene may be carried out in the presence of active chlorinating species The chlorine partial pressure was found to have an appreciable effect on the system reactivity. The temperature was found to be the most important variable affecting the reaction rate. The β-spodumene chlorination process by Cl2 was characterized by an apparent activation energy of about 359 kJ/mol in the range from 1000 to 1100 °C. Reaction was of non-catalytic gas–solid nature and experimental data fitted the sequential nucleation and growth model.
An hourly simulation program has been developed for detailed modeling of an evaporation surface (ES) and an evaporation pond (EP) for reconcentration of a solar pond's (SP's) surface brine. The results are relevant to other systems in which it is desirable to concentrate a brine. The simulation results are used in three ways: first, for a general comparison of brine reconcentration performance for a variety of locations; second, development of an ES design method based on long term monthly averaged weather data; and third, an economic comparison between ESs and EPs. The results show that regions with moderate to high precipitation favor ESs over EPs. Dry climates will generally favor EPs for brine reconcentration.
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.
The structure of a lepidolite-2 M 1 from Biskupice, Czechoslovakia, has been redetermined. Violations of systematic extinctions and of monoclinic equivalences plus the results of a second harmonic generation test indicate that the true symmetry most likely is C 1̄. The deviation of the data set from C 2/ c symmetry, however, proved to be too small to permit a statistically significant refinement in C 1̄. Refinement in C 2/ c symmetry indicated no ordering of tetrahedral cations but ordering of octahedral cations so that M(1) = Li 0.93 R ²⁺ 0.06 Fe ³⁺ 0.01 and M(2) = Al 0.58 Li 0.35 □ 0.07 . The tetrahedra are elongated to form trigonal pyramids with a rotation angle of 6.2°. The anomalous orientation of the thermal ellipsoid for the F,OH anion plus the large equivalent isotropic B value of 2.58 for F,OH and of 1.74 for the interlayer K cation, whose position is partly restricted in C 2/ c symmetry, suggest a lower symmetry than C 2/ c .
The compositions of this sample and of a second lepidolite-2 M 1 from Western Australia fall outside the stability field of lepidolite-2 M 1 in the synthetic system. Structural control of the stacking sequence is discounted on the basis of the structural similarity of the lepidolite unit layers. Crystallization parameters are considered more important than composition or the structure of the unit layer in determining the stability and occurrence of different layer-stacking sequences in lepidolite.
By evaporation employing solar energy, a brine having a lithium chloride concentration greater than that of a brine whose vapor pressure under ambient conditions is substantially equal to the partial pressure of moisture in the atmosphere above the brine is obtained. The process by which such result is accomplished involves the use of a pond system consisting of a series of shallow ponds of relatively large surface area to which a dilute lithium chloride brine is introduced. The flow of the brine through the pond system is controlled so that, at a point intermediate the points of introduction of the brine to and withdrawal of the brine from the pond system, the concentration of the brine is such that its vapor pressure under ambient conditions is substantially equal to the partial pressure of the moisture in the atmosphere immediately above the pond system. This more concentrated brine is then caused to flow through the remainder of the pond system at a rate such that the temperature thereof, as a result of exposure to solar energy, exceeds that of the atmosphere above the pond system whereby additional water is evaporated from the brine to further increase the lithium chloride concentration of the brine. The concentrated lithium chloride brine is recovered and may be used to generate impure lithium chloride monohydrate or further purified to provide relatively pure anhydrous lithium chloride or the monohydrate.