This research optimized the structure of lithium extraction solar ponds to enhance the crystallization rate and yield of Li_(2)CO_(3).Using the response surface methodology in Design-Expert 10.0.3,the authors conducte...This research optimized the structure of lithium extraction solar ponds to enhance the crystallization rate and yield of Li_(2)CO_(3).Using the response surface methodology in Design-Expert 10.0.3,the authors conducted experiments to investigate the influence of four factors related to solar pond structure on the crystallization of Li_(2)CO_(3) and their pairwise interactions.Computational Fluid Dynamics(CFD)simulations of the flow field within the solar pond were performed using COMSOL Multiphysics software to compare temperature distributions before and after optimization.The results indicate that the optimal structure for lithium extraction from the Zabuye Salt Lake solar ponds includes UCZ(Upper Convective Zone)thickness of 53.63 cm,an LCZ(Lower Convective Zone)direct heating temperature of 57.39℃,a CO32−concentration of 32.21 g/L,and an added soda ash concentration of 6.52 g/L.Following this optimized pathway,the Li_(2)CO_(3) precipitation increased by 7.34% compared to the initial solar pond process,with a 33.33% improvement in lithium carbonate crystallization rate.This study demonstrates the feasibility of optimizing lithium extraction solar pond structures,offering a new approach for constructing such ponds in salt lakes.It provides valuable guidance for the efficient extraction of lithium resources from carbonate-type salt lake brines.展开更多
A roasting-leaching test was carried out for the efficient utilization of clay-type lithium ore in the central region of Yunnan province.The test used the mixed acid of sulfuric acid and phosphoric acid as the leachin...A roasting-leaching test was carried out for the efficient utilization of clay-type lithium ore in the central region of Yunnan province.The test used the mixed acid of sulfuric acid and phosphoric acid as the leaching agent.Under the conditions of roasting temperature of 600℃,roasting time of 1 h,liquid-solid ratio of 5:1,volume ratio of H_(2)SO_(4)solution to H_(3)PO_(4)solution of 45:5,leaching time of 2 h and leaching temperature of 80℃,the leaching rate of lithium was as high as 97.83%.The leaching mechanism was studied by SEM,pore property analysis,XRD and XPS.It was found that the morphology of the ore changed obviously after roasting and leaching,and a certain degree of collapse and fragmentation occurred,which provided favorable spatial conditions for the leaching of lithium.The porosity,total intrusion volume and total pore area also increased after roasting and leaching,thus promoting the leaching of Li^(+).The results showed that chemical reaction taken placed during the roasting and leaching.The phase of the sample changed from chlorite,kaolinite and diaspore(boehmite)mainly to corundum,hematite,periclase and quartz after roasting.However,after leaching,no new phase was produced in the ore sample,and no S and P elements were found on the surface of the ore sample,indicating that the leaching mechanism of lithium might be the ion exchange between H^(+)and Li^(+).展开更多
Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selectiv...Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.展开更多
Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines gi...Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.展开更多
In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited pr...In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs.This work introduces a novel approach to the manganese-titanium based composite HMTO(Mn:Ti=1:4)lithium ion-sieve(LIS)nanospheres,employing lithium acetate dihydrate,manganese carbonate and titanium dioxide P25 as the primary materials.These nanospheres exhibit relatively uniform spherical morphology,narrow size distribution,small average particle size(ca.55 nm),large specific surface area(43.58 m^(2)g^(-1))and high surface O_(2)-content(59.01%).When utilized as the adsorbents for Li^(+)ions,the HMTO(Mn:Ti=1:4)LIS demonstrates a fast adsorption rate,approaching equilibrium within 6.0 h with an equilibrium adsorption capacity(qe)of 79.5 mg g^(-1)and a maximum adsorption capacity(qm)of 87.26 mg g^(-1)(initial concentration CO:1.8 g L^(-1)).In addition,the HMTO(Mn:Ti=1:4)also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine(Mg:Li=103),achieving a qeof 33.85 mg g^(-1)along with a remarkable selectivity(α_(Mg)^(Li)=2192.76).Particularly,the HMTO(Mn:Ti=1:4)LIS showcases a satisfactory recycling adsorption performance.The adsorption capacity remains at a high level,even that determined after the 5th cycle(55.45 mg g^(-1))surpasses that of the most recently reported adsorbents.Ultimately,the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics(MD)simulations.展开更多
Salt lake brine was reacted with activated aluminum-based alloys and lithium was precipitated.The effects of aluminum-based alloys on precipitating lithium were investigated and the reasonable alloy used to extract li...Salt lake brine was reacted with activated aluminum-based alloys and lithium was precipitated.The effects of aluminum-based alloys on precipitating lithium were investigated and the reasonable alloy used to extract lithium from brine was obtained.The effects of the mole ratio of Al to Li and Ca content of Al-Ca alloy,the initial concentration of lithiumion ion in solution,reaction temperature and reaction time on the adsorption rate of lithium were studied,and the optimized process parameters were determined.The results show that the mole ratio of Al to Li and Ca content of Al-Ca alloy and reaction temperature have great influences on the precipitation rate of lithium.The precipitation rate of lithium reaches 94.6% under the optimal condition,indicating that Al-Ca alloy is suitable for the extraction of lithium from salt lake brine.展开更多
In this paper,a lithium-ion sieve(LIS)with different morphologies,such as rod-like(LIS-R),spherical(LIS-S),flower-like(LIS-F),and three-dimensional macroporous-mesoporous(LIS-3D),was prepared by hydrothermal synthesis...In this paper,a lithium-ion sieve(LIS)with different morphologies,such as rod-like(LIS-R),spherical(LIS-S),flower-like(LIS-F),and three-dimensional macroporous-mesoporous(LIS-3D),was prepared by hydrothermal synthesis,solid reaction,and hard-template synthesis.The results showed that the LIS with different morphologies presented great differences in specific surface area,pore volume,adsorption selectivity,and structure stability.LIS-3D with highest specific surface area and pore volume displayed the maximum adsorption capacity and adsorption rate,but the stability of LIS-3D was poor because of the manganese dissolution.By comparison,LIS-S has the best structural stability while maintaining a satisfactory adsorption capacity(35.02 mg·g^(-1))and adsorption rate.The LIS-S remained about 90%of the original adsorption capacity after five cycles of adsorption-desorption process.In addition,in the simulated brine system(the magnesium to lithium ratio of 400),the LIS-S exhibited the highest selectivity(α_(Mg)^(Li))of 425.14.In sum,the LIS-S with good morphology is a potential adsorbent for lithium extraction from brine.展开更多
Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of sp...Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of spent LiFePO_(4)power batteries have been scrapped and entered the recycling stage.Herein,a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO_(4)powder without any treatment.Various electrochemical test results show that spent LiFePO_(4)electrode has appropriate lithium capacity(14.62 mg_(Li)/g_(LiFePO_(4))),excellent separation performance(α_(Li-Na)=210.5)and low energy consumption(0.768 Wh/g_(Li))in electrochemical lithium extraction from simulated brine.This work not only provides a novel idea for lithium extraction from brine,but also develops an effective strategy for recycling spent LIBs.The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.展开更多
Lithium production in China mainly depends on hard rock lithium ores,which has a defect in resources,environment,and economy compared with extracting lithium from brine.This paper focuses on the research progress of e...Lithium production in China mainly depends on hard rock lithium ores,which has a defect in resources,environment,and economy compared with extracting lithium from brine.This paper focuses on the research progress of extracting lithium from spodumene,lepidolite,petalite,and zinnwaldite by acid,alkali,salt roasting,and chlorination methods,and analyzes the resource intensity,environmental impact,and production cost of industrial lithium extraction from spodumene and lepidolite.It is found that the sulfuric acid method has a high lithium recovery rate,but with a complicated process and high energy consumption;alkali and chlorination methods can directly react with lithium ores,reducing energy consumption,but need to optimize reaction conditions and safety of equipment and operation;the salt roasting method has large material flux and high energy consumption,so require adjustment of sulfate ratio to increase the lithium yield and reduce production cost.Compared with extracting lithium from brine,extracting lithium from ores,calcination,roasting,purity,and other processes consume more resources and energy;and its environmental impact mainly comes from the pollutants discharged by fossil energy,9.3-60.4 times that of lithium extracted from brine.The processing cost of lithium extraction from lepidolite by sulfate roasting method is higher than that from spodumene by sulfuric acid due to the consumption of high-value sulfate.However,the production costs of both are mainly affected by the price of lithium ores,which is less competitive than that of extracting lithium from brine.Thus,the process of extracting lithium from ores should develop appropriate technology,shorten the process flow,save resources and energy,and increase the recovery rate of related elements to reduce environmental impact and improve the added value of by-products and the economy of the process.展开更多
The demand for lithium resources is increasing sharply with the rapid development of electric vehicles.It is of great economic significance to expand the geological resources of lithium and improve the utilization rat...The demand for lithium resources is increasing sharply with the rapid development of electric vehicles.It is of great economic significance to expand the geological resources of lithium and improve the utilization rate of lithium-containing salt lakes.In this paper,the hydrochemical types of the lithium-containing salt lakes in the Tibet Plateau were classified according to a large amount of hydrochemical data obtained from a recent investigation on the Tibet Plateau.In addition,the lithium extraction methods used in the salt lakes within each hydrochemical type area were analyzed and summarized,which provided a reference for the selection of lithium extraction processes in the same hydrochemical type of lithium-containing salt lakes in the future.The binding energies of Li(l)and anions in salt lakes with different hydrochemical types were calculated by density functional theory,which provides the theoretical basis for selecting the best lithium extraction technology in different salt lakes.We emphasize that the process with the combined characteristics of high efficiency,economy and environmental protection should be selected according to the hydrochemical type of different salt lakes.In the future,different salt lakes should focus on direct lithium extraction technology from the original brine.展开更多
The global carbon neutrality strategy brings a wave of rechargeable lithium‐ion batteries technique development and induces an ever-growing consumption and demand for lithium(Li).Among all the Li exploitation,extract...The global carbon neutrality strategy brings a wave of rechargeable lithium‐ion batteries technique development and induces an ever-growing consumption and demand for lithium(Li).Among all the Li exploitation,extracting Li from spent LIBs would be a strategic and perspective approach,especially with the low energy consumption and eco-friendly membrane separation method.However,current membrane separation systems mainly focus on monotonous membrane design and structure optimization,and rarely further consider the coordination of inherent structure and applied external field,resulting in limited ion transport.Here,we propose a heterogeneous nanofluidic membrane as a platform for coupling multi-external fields(i.e.,lightinduced heat,electrical,and concentration gradient fields)to construct the multi-field-coupled synergistic ion transport system(MSITS)for Li-ion extraction from spent LIBs.The Li flux of the MSITS reaches 367.4 mmol m^(−2)h^(−1),even higher than the sum flux of those applied individual fields,reflecting synergistic enhancement for ion transport of the multi-field-coupled effect.Benefiting from the adaptation of membrane structure and multi-external fields,the proposed system exhibits ultrahigh selectivity with a Li^(+)/Co^(2+)factor of 216,412,outperforming previous reports.MSITS based on nanofluidic membrane proves to be a promising ion transport strategy,as it could accelerate ion transmembrane transport and alleviate the ion concentration polarization effect.This work demonstrated a collaborative system equipped with an optimized membrane for high-efficient Li extraction,providing an expanded strategy to investigate the other membrane-based applications of their common similarities in core concepts.展开更多
The extraction of lithium from salt lake brine in the Chinese Qaidam Basin is challenging due to its high Mg/Li and Na/Li ratios. Herein, we utilized a reaction-coupled separation technology to separate sodium and lit...The extraction of lithium from salt lake brine in the Chinese Qaidam Basin is challenging due to its high Mg/Li and Na/Li ratios. Herein, we utilized a reaction-coupled separation technology to separate sodium and lithium ions from a high Na/Li ratio brine(Na/Li = 48.7, w/w) and extracted lithium with Li Al-layered double hydroxides(Li Al-LDHs). The Li Al-LDHs act as lithium-ion-selective capturing materials from multication brines. That is, the lithium ions selectively enter the solid phase to form Li Al-LDHs, and the sodium ions are still retained in the liquid phase. This is because the lithium ions can be incorporated into the structural vacancies of LiAl-LDHs, whereas the sodium ions cannot. The effects of reaction conditions on lithium loss and separation efficiency were investigated at both the nucleation and the crystallization stage, e.g., the nucleation rotating speed, the Li/Al molar ratio, the crystallization temperature and time, and co-existing cations. The lithium loss is as low as 3.93% under optimal separation conditions.The sodium ions remained in the solution. Consequently, an excellent Na/Li separation efficiency was achieved by this reaction-coupled separation technology. These findings confirm that LiAl-LDHs play a critical function in selectively capturing lithium ions from brines with a high Na/Li ratio, which is useful for the extraction of lithium ions from the abundant salt lake brine resources in China.展开更多
AI（OH）3 was prepared to extract lithium ions from calcium chloride-type oil field brine. The influences of four factors, namely temperature, Al3＋/Li＋ molar ratio, OH-/Al3＋ molar ratio, and contact time between AI...AI（OH）3 was prepared to extract lithium ions from calcium chloride-type oil field brine. The influences of four factors, namely temperature, Al3＋/Li＋ molar ratio, OH-/Al3＋ molar ratio, and contact time between AI（OH）3 and the brine, on the yield of lithium ions were investigated. It is found that their optimal values are 35℃, 4.5, 2.6, and 6 h, respectively. In the course of the experiment, the apparent pH value was observed. The results reveal that the apparent pH value has no remarkable influence on the yield of lithium ions. Meanwhile, the effects of the concentrations of calcium ions and magnesium ions in the brine on lithium recovery were studied. The results indicate that cal- cium ions have minor negative influence on the yield of lithium ions under optimal conditions, and magnesium ions slightly influence the yield of lithium ions.展开更多
A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous n...A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous novel lithium resources. Given the presence of varied classification criteria for lithium resources presently, this study further ascertained and classified the lithium resources according to their occurrence modes, obtaining 10 types and 5 subtypes of lithium deposits(resources) based on endogenetic and exogenetic factors. As indicated by surveys of Cenozoic exogenetic lithium deposits in China and abroad,the formation and distribution of the deposits are primarily determined by plate collision zones, their primary material sources are linked to the anatectic magmas in the deep oceanic crust, and they were formed primarily during the Miocene and Late Paleogene. The researchers ascertained that these deposits,especially those of the salt lake, geothermal, and volcanic deposit types, are formed by unique slightly acidic magmas, tend to migrate and accumulate toward low-lying areas, and display supernormal enrichment. However, the material sources of lithium deposits(resources) of the Neopaleozoic clay subtype and the deep brine type are yet to be further identified. Given the various types and complex origins of lithium deposits(resources), which were formed due to the interactions of multiple spheres, it is recommended that the mineralization of exogenetic lithium deposits(resources) be investigated by integrating tectono-geochemistry, paleoatmospheric circulation, and salinology. So far, industrialized lithium extraction is primarily achieved in lithium deposits of the salt lake, clay, and hard rock types. The lithium extraction employs different processes, with lithium extraction from salt lake-type lithium deposits proving the most energy-saving and cost-effective.展开更多
With the worldwide rise in electric vehicles, the demand for lithium batteries is increasing day by day. In 2015, China＇s new energy vehicles developed rapidly, and the price of lithium carbonate rose from fifty or s...With the worldwide rise in electric vehicles, the demand for lithium batteries is increasing day by day. In 2015, China＇s new energy vehicles developed rapidly, and the price of lithium carbonate rose from fifty or sixty thousand yuan per ton to 150 thousand yuan. In the past, lithium was often extracted from spodumene （LiAlSi2O6）, which is time consuming, laborious and expensive. Over the past decade, abundant lithium has been discovered in brackish and salt water lakes, which is an important way to obtain lithium resources.展开更多
Tri-n-butyl phosphate（TBP）dissolved in kerosene was chosen as extractant for lithium from a modelbrine having high magnesium-to-lithium ratio and ferric chloride was added to the system.The influences of con-tact ti...Tri-n-butyl phosphate（TBP）dissolved in kerosene was chosen as extractant for lithium from a modelbrine having high magnesium-to-lithium ratio and ferric chloride was added to the system.The influences of con-tact time,concentration of the extractant,concentrations of some salts(Mg<sup>2+</sup>, Na<sup>+</sup>,K<sup>+</sup>)in the solution,acid-ity of hydrochloric acid and extraction temperature on the exttaction of lithium with TBP-kerosene system werestudied.The suitable extraction conditions were found to be:contact time not any less than 20min;at 20-25C;[Fe<sup>+3</sup>]/[Li<sup>+</sup>]about 1.5-2.0;TBP concentration 50%-70%;[MgCl<sub>2</sub>]exceeding 3 mol·L<sup>-1</sup>;pH about 2;while most sodium and potassium salts in the aqueous phase should be removed before the extraction.展开更多
In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) dur...In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.展开更多
For the development of lithium ion recovery process from seawater, a series of experimental researches were performed. Solvent extraction of lithium ion from aqueous solution using kerosene as solvent was proposed. Li...For the development of lithium ion recovery process from seawater, a series of experimental researches were performed. Solvent extraction of lithium ion from aqueous solution using kerosene as solvent was proposed. Lithium ion is effectively extracted by thenoyltrifluoroace- tone-trioctylphosphine oxide （TTA-TOPO） in kerosene within 80 min. Extraction efficiency is severely influenced by stoichiometric parameters. Among the stoichiometric parameters, volume ratio of aqueous （A） to extraction （E） solution is the most influential parameter. After extrac- tion, lithium ion could be easily stripped from the extraction solution by acidic solutions. Stripping efficiency decreases with pH of acidic solutions, and the kind of acid does not affect the stripping efficiency. Extraction efficiency main- tains at more than 93 % even when the extraction solution is recycled three times. 65 % of lithium ion can be extracted from seawater by this solvent extraction process when magnesium ion is precipitated by NHaOH prior to solvent extraction process. Other metallic ions in seawater decrease the extraction efficiency of lithium ion.展开更多
1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fie...1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fields,especially in展开更多
The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. There- fore, this study optimized an innovative process, which does not require a high-temperatu...The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. There- fore, this study optimized an innovative process, which does not require a high-temperature calcination step, for lithium extraction from le- pidolite. Mechanical activation and acid digestion were suggested as crucial process parameters, and experimental design and re- sponse-surface methodology were applied to model and optimize the proposed lithium extraction process. The promoting effect of amorphi- zation and the formation of lithium sulfate hydrate on lithium extraction yield were assessed. Several factor combinations led to extraction yields that exceeded 90%, indicating that the proposed process is an effective approach for lithium recovery.展开更多
基金This study was supported by the National Natural Science Foundation of China(U20A20148)the Major Science and Technology Projects of the Xizang(Tibet)Autonomous Region(XZ202201ZD0004G and XZ202201ZD0004G01).
文摘This research optimized the structure of lithium extraction solar ponds to enhance the crystallization rate and yield of Li_(2)CO_(3).Using the response surface methodology in Design-Expert 10.0.3,the authors conducted experiments to investigate the influence of four factors related to solar pond structure on the crystallization of Li_(2)CO_(3) and their pairwise interactions.Computational Fluid Dynamics(CFD)simulations of the flow field within the solar pond were performed using COMSOL Multiphysics software to compare temperature distributions before and after optimization.The results indicate that the optimal structure for lithium extraction from the Zabuye Salt Lake solar ponds includes UCZ(Upper Convective Zone)thickness of 53.63 cm,an LCZ(Lower Convective Zone)direct heating temperature of 57.39℃,a CO32−concentration of 32.21 g/L,and an added soda ash concentration of 6.52 g/L.Following this optimized pathway,the Li_(2)CO_(3) precipitation increased by 7.34% compared to the initial solar pond process,with a 33.33% improvement in lithium carbonate crystallization rate.This study demonstrates the feasibility of optimizing lithium extraction solar pond structures,offering a new approach for constructing such ponds in salt lakes.It provides valuable guidance for the efficient extraction of lithium resources from carbonate-type salt lake brines.
基金supported by Yunnan Fundamental Research Projects(grant No.202201BE070001-016)project from Technology Innovation Center for Comprehensive Utilization of Strategic Mineral Resources,Ministry of Natural Resources(grant No.CCUM-KY-2308)+1 种基金National Natural Science Foundation of China(grant No.52304288)project“Study on high efficiency utilization of multicomponent in clay lithium ore with low temperature roasting”from Xing Dian Talent Program of Yunnan province.
文摘A roasting-leaching test was carried out for the efficient utilization of clay-type lithium ore in the central region of Yunnan province.The test used the mixed acid of sulfuric acid and phosphoric acid as the leaching agent.Under the conditions of roasting temperature of 600℃,roasting time of 1 h,liquid-solid ratio of 5:1,volume ratio of H_(2)SO_(4)solution to H_(3)PO_(4)solution of 45:5,leaching time of 2 h and leaching temperature of 80℃,the leaching rate of lithium was as high as 97.83%.The leaching mechanism was studied by SEM,pore property analysis,XRD and XPS.It was found that the morphology of the ore changed obviously after roasting and leaching,and a certain degree of collapse and fragmentation occurred,which provided favorable spatial conditions for the leaching of lithium.The porosity,total intrusion volume and total pore area also increased after roasting and leaching,thus promoting the leaching of Li^(+).The results showed that chemical reaction taken placed during the roasting and leaching.The phase of the sample changed from chlorite,kaolinite and diaspore(boehmite)mainly to corundum,hematite,periclase and quartz after roasting.However,after leaching,no new phase was produced in the ore sample,and no S and P elements were found on the surface of the ore sample,indicating that the leaching mechanism of lithium might be the ion exchange between H^(+)and Li^(+).
基金the Science and Technology Key Project of Anhui Province,China(No.2022e03020004).
文摘Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.
基金financially supported by the National Natural Science Foundation of China(No.52072322)the Department of Science and Technology of Sichuan Province,China(Nos.23GJHZ0147,23ZDYF0262,2022YFG0294,and 2019-GH02-00052-HZ)。
文摘Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.
基金supported by the National Natural Science Foundation of China(22075304,22378390)Natural Science Foundation of Shandong Province,China(ZR2022MB075)+2 种基金State Key Laboratory of Organic-Inorganic Composites(oic-202401016)State Key Laboratory of Chemical Engineering(SKL-ChE-24A02)Beijing Natural Science Foundation,China(3222050).
文摘In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains,conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs.This work introduces a novel approach to the manganese-titanium based composite HMTO(Mn:Ti=1:4)lithium ion-sieve(LIS)nanospheres,employing lithium acetate dihydrate,manganese carbonate and titanium dioxide P25 as the primary materials.These nanospheres exhibit relatively uniform spherical morphology,narrow size distribution,small average particle size(ca.55 nm),large specific surface area(43.58 m^(2)g^(-1))and high surface O_(2)-content(59.01%).When utilized as the adsorbents for Li^(+)ions,the HMTO(Mn:Ti=1:4)LIS demonstrates a fast adsorption rate,approaching equilibrium within 6.0 h with an equilibrium adsorption capacity(qe)of 79.5 mg g^(-1)and a maximum adsorption capacity(qm)of 87.26 mg g^(-1)(initial concentration CO:1.8 g L^(-1)).In addition,the HMTO(Mn:Ti=1:4)also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine(Mg:Li=103),achieving a qeof 33.85 mg g^(-1)along with a remarkable selectivity(α_(Mg)^(Li)=2192.76).Particularly,the HMTO(Mn:Ti=1:4)LIS showcases a satisfactory recycling adsorption performance.The adsorption capacity remains at a high level,even that determined after the 5th cycle(55.45 mg g^(-1))surpasses that of the most recently reported adsorbents.Ultimately,the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics(MD)simulations.
基金Project(U1407137)supported by the National Natural Science Foundation of China
文摘Salt lake brine was reacted with activated aluminum-based alloys and lithium was precipitated.The effects of aluminum-based alloys on precipitating lithium were investigated and the reasonable alloy used to extract lithium from brine was obtained.The effects of the mole ratio of Al to Li and Ca content of Al-Ca alloy,the initial concentration of lithiumion ion in solution,reaction temperature and reaction time on the adsorption rate of lithium were studied,and the optimized process parameters were determined.The results show that the mole ratio of Al to Li and Ca content of Al-Ca alloy and reaction temperature have great influences on the precipitation rate of lithium.The precipitation rate of lithium reaches 94.6% under the optimal condition,indicating that Al-Ca alloy is suitable for the extraction of lithium from salt lake brine.
基金National Natural Science Foundation of China,(Grant No.21868031)。
文摘In this paper,a lithium-ion sieve(LIS)with different morphologies,such as rod-like(LIS-R),spherical(LIS-S),flower-like(LIS-F),and three-dimensional macroporous-mesoporous(LIS-3D),was prepared by hydrothermal synthesis,solid reaction,and hard-template synthesis.The results showed that the LIS with different morphologies presented great differences in specific surface area,pore volume,adsorption selectivity,and structure stability.LIS-3D with highest specific surface area and pore volume displayed the maximum adsorption capacity and adsorption rate,but the stability of LIS-3D was poor because of the manganese dissolution.By comparison,LIS-S has the best structural stability while maintaining a satisfactory adsorption capacity(35.02 mg·g^(-1))and adsorption rate.The LIS-S remained about 90%of the original adsorption capacity after five cycles of adsorption-desorption process.In addition,in the simulated brine system(the magnesium to lithium ratio of 400),the LIS-S exhibited the highest selectivity(α_(Mg)^(Li))of 425.14.In sum,the LIS-S with good morphology is a potential adsorbent for lithium extraction from brine.
基金supported by the National Natural Science Foundation of China(Nos.52173246,91963118,and 52102213)the Science Technology Program of Jilin Province(No.20200201066JC)。
文摘Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of spent LiFePO_(4)power batteries have been scrapped and entered the recycling stage.Herein,a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO_(4)powder without any treatment.Various electrochemical test results show that spent LiFePO_(4)electrode has appropriate lithium capacity(14.62 mg_(Li)/g_(LiFePO_(4))),excellent separation performance(α_(Li-Na)=210.5)and low energy consumption(0.768 Wh/g_(Li))in electrochemical lithium extraction from simulated brine.This work not only provides a novel idea for lithium extraction from brine,but also develops an effective strategy for recycling spent LIBs.The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.
基金financially supported by the National Natural Science Foundation of China(71991484,41971265,72088101,and 71991480)the National Key R&D program of China(2021YFC2901801)。
文摘Lithium production in China mainly depends on hard rock lithium ores,which has a defect in resources,environment,and economy compared with extracting lithium from brine.This paper focuses on the research progress of extracting lithium from spodumene,lepidolite,petalite,and zinnwaldite by acid,alkali,salt roasting,and chlorination methods,and analyzes the resource intensity,environmental impact,and production cost of industrial lithium extraction from spodumene and lepidolite.It is found that the sulfuric acid method has a high lithium recovery rate,but with a complicated process and high energy consumption;alkali and chlorination methods can directly react with lithium ores,reducing energy consumption,but need to optimize reaction conditions and safety of equipment and operation;the salt roasting method has large material flux and high energy consumption,so require adjustment of sulfate ratio to increase the lithium yield and reduce production cost.Compared with extracting lithium from brine,extracting lithium from ores,calcination,roasting,purity,and other processes consume more resources and energy;and its environmental impact mainly comes from the pollutants discharged by fossil energy,9.3-60.4 times that of lithium extracted from brine.The processing cost of lithium extraction from lepidolite by sulfate roasting method is higher than that from spodumene by sulfuric acid due to the consumption of high-value sulfate.However,the production costs of both are mainly affected by the price of lithium ores,which is less competitive than that of extracting lithium from brine.Thus,the process of extracting lithium from ores should develop appropriate technology,shorten the process flow,save resources and energy,and increase the recovery rate of related elements to reduce environmental impact and improve the added value of by-products and the economy of the process.
基金the National Natural Science Foundation of China for financial support(No.91962219).
文摘The demand for lithium resources is increasing sharply with the rapid development of electric vehicles.It is of great economic significance to expand the geological resources of lithium and improve the utilization rate of lithium-containing salt lakes.In this paper,the hydrochemical types of the lithium-containing salt lakes in the Tibet Plateau were classified according to a large amount of hydrochemical data obtained from a recent investigation on the Tibet Plateau.In addition,the lithium extraction methods used in the salt lakes within each hydrochemical type area were analyzed and summarized,which provided a reference for the selection of lithium extraction processes in the same hydrochemical type of lithium-containing salt lakes in the future.The binding energies of Li(l)and anions in salt lakes with different hydrochemical types were calculated by density functional theory,which provides the theoretical basis for selecting the best lithium extraction technology in different salt lakes.We emphasize that the process with the combined characteristics of high efficiency,economy and environmental protection should be selected according to the hydrochemical type of different salt lakes.In the future,different salt lakes should focus on direct lithium extraction technology from the original brine.
基金supported by the National Key R&D Program of China(2022YFB3805904,2022YFB3805900)the National Natural Science Foundation of China(22122207,21988102,21905287)CAS Project for Young Scientists in Basic Research(YSBR-039).
文摘The global carbon neutrality strategy brings a wave of rechargeable lithium‐ion batteries technique development and induces an ever-growing consumption and demand for lithium(Li).Among all the Li exploitation,extracting Li from spent LIBs would be a strategic and perspective approach,especially with the low energy consumption and eco-friendly membrane separation method.However,current membrane separation systems mainly focus on monotonous membrane design and structure optimization,and rarely further consider the coordination of inherent structure and applied external field,resulting in limited ion transport.Here,we propose a heterogeneous nanofluidic membrane as a platform for coupling multi-external fields(i.e.,lightinduced heat,electrical,and concentration gradient fields)to construct the multi-field-coupled synergistic ion transport system(MSITS)for Li-ion extraction from spent LIBs.The Li flux of the MSITS reaches 367.4 mmol m^(−2)h^(−1),even higher than the sum flux of those applied individual fields,reflecting synergistic enhancement for ion transport of the multi-field-coupled effect.Benefiting from the adaptation of membrane structure and multi-external fields,the proposed system exhibits ultrahigh selectivity with a Li^(+)/Co^(2+)factor of 216,412,outperforming previous reports.MSITS based on nanofluidic membrane proves to be a promising ion transport strategy,as it could accelerate ion transmembrane transport and alleviate the ion concentration polarization effect.This work demonstrated a collaborative system equipped with an optimized membrane for high-efficient Li extraction,providing an expanded strategy to investigate the other membrane-based applications of their common similarities in core concepts.
基金supported by the National Natural Science Foundation of China (Grant U1507202, U1707603)the Innovative Research Groups of National Natural Science Foundation of China (Grant 21521005)the Key R&D Program of Qinghai Province (Grant 2017-GX-144)
文摘The extraction of lithium from salt lake brine in the Chinese Qaidam Basin is challenging due to its high Mg/Li and Na/Li ratios. Herein, we utilized a reaction-coupled separation technology to separate sodium and lithium ions from a high Na/Li ratio brine(Na/Li = 48.7, w/w) and extracted lithium with Li Al-layered double hydroxides(Li Al-LDHs). The Li Al-LDHs act as lithium-ion-selective capturing materials from multication brines. That is, the lithium ions selectively enter the solid phase to form Li Al-LDHs, and the sodium ions are still retained in the liquid phase. This is because the lithium ions can be incorporated into the structural vacancies of LiAl-LDHs, whereas the sodium ions cannot. The effects of reaction conditions on lithium loss and separation efficiency were investigated at both the nucleation and the crystallization stage, e.g., the nucleation rotating speed, the Li/Al molar ratio, the crystallization temperature and time, and co-existing cations. The lithium loss is as low as 3.93% under optimal separation conditions.The sodium ions remained in the solution. Consequently, an excellent Na/Li separation efficiency was achieved by this reaction-coupled separation technology. These findings confirm that LiAl-LDHs play a critical function in selectively capturing lithium ions from brines with a high Na/Li ratio, which is useful for the extraction of lithium ions from the abundant salt lake brine resources in China.
基金supported by the Ministry of Science and Technology of People's Republic of China (No.2006BAB09B07)National Nature Science Foundation of China (No.41073023)Research Project of Science and Technology Department of Qinghai Province, China (No.2010-G-210)
文摘AI（OH）3 was prepared to extract lithium ions from calcium chloride-type oil field brine. The influences of four factors, namely temperature, Al3＋/Li＋ molar ratio, OH-/Al3＋ molar ratio, and contact time between AI（OH）3 and the brine, on the yield of lithium ions were investigated. It is found that their optimal values are 35℃, 4.5, 2.6, and 6 h, respectively. In the course of the experiment, the apparent pH value was observed. The results reveal that the apparent pH value has no remarkable influence on the yield of lithium ions. Meanwhile, the effects of the concentrations of calcium ions and magnesium ions in the brine on lithium recovery were studied. The results indicate that cal- cium ions have minor negative influence on the yield of lithium ions under optimal conditions, and magnesium ions slightly influence the yield of lithium ions.
基金funded by the major research program of the of National Natural Science Foundation of China entitled Metallogenic Mechanisms and Regularity of the Lithium Ore Concentration Area in the Zabuye Salt Lake, Tibet (91962219)Science and Technology Major Project of the Tibet Autonomous Region ’s Science and Techonlogy Plan (XZ202201ZD0004G01)a geological survey project of China Geological Survey (DD20230037)。
文摘A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous novel lithium resources. Given the presence of varied classification criteria for lithium resources presently, this study further ascertained and classified the lithium resources according to their occurrence modes, obtaining 10 types and 5 subtypes of lithium deposits(resources) based on endogenetic and exogenetic factors. As indicated by surveys of Cenozoic exogenetic lithium deposits in China and abroad,the formation and distribution of the deposits are primarily determined by plate collision zones, their primary material sources are linked to the anatectic magmas in the deep oceanic crust, and they were formed primarily during the Miocene and Late Paleogene. The researchers ascertained that these deposits,especially those of the salt lake, geothermal, and volcanic deposit types, are formed by unique slightly acidic magmas, tend to migrate and accumulate toward low-lying areas, and display supernormal enrichment. However, the material sources of lithium deposits(resources) of the Neopaleozoic clay subtype and the deep brine type are yet to be further identified. Given the various types and complex origins of lithium deposits(resources), which were formed due to the interactions of multiple spheres, it is recommended that the mineralization of exogenetic lithium deposits(resources) be investigated by integrating tectono-geochemistry, paleoatmospheric circulation, and salinology. So far, industrialized lithium extraction is primarily achieved in lithium deposits of the salt lake, clay, and hard rock types. The lithium extraction employs different processes, with lithium extraction from salt lake-type lithium deposits proving the most energy-saving and cost-effective.
文摘With the worldwide rise in electric vehicles, the demand for lithium batteries is increasing day by day. In 2015, China＇s new energy vehicles developed rapidly, and the price of lithium carbonate rose from fifty or sixty thousand yuan per ton to 150 thousand yuan. In the past, lithium was often extracted from spodumene （LiAlSi2O6）, which is time consuming, laborious and expensive. Over the past decade, abundant lithium has been discovered in brackish and salt water lakes, which is an important way to obtain lithium resources.
文摘Tri-n-butyl phosphate（TBP）dissolved in kerosene was chosen as extractant for lithium from a modelbrine having high magnesium-to-lithium ratio and ferric chloride was added to the system.The influences of con-tact time,concentration of the extractant,concentrations of some salts(Mg<sup>2+</sup>, Na<sup>+</sup>,K<sup>+</sup>)in the solution,acid-ity of hydrochloric acid and extraction temperature on the exttaction of lithium with TBP-kerosene system werestudied.The suitable extraction conditions were found to be:contact time not any less than 20min;at 20-25C;[Fe<sup>+3</sup>]/[Li<sup>+</sup>]about 1.5-2.0;TBP concentration 50%-70%;[MgCl<sub>2</sub>]exceeding 3 mol·L<sup>-1</sup>;pH about 2;while most sodium and potassium salts in the aqueous phase should be removed before the extraction.
基金National Key Research and Development Program of China(No.2018YFC0604800)National Natural Science Foundation of China(No.U1707601)+1 种基金Science and Technology Major Project of Qinghai Province(2019-GX-A5)West Light Talent Program of Chines Academy of Sciences(Doctor Project,2016)
文摘In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.
基金financially supported by the Research Grant of Pukyong National University (2014)
文摘For the development of lithium ion recovery process from seawater, a series of experimental researches were performed. Solvent extraction of lithium ion from aqueous solution using kerosene as solvent was proposed. Lithium ion is effectively extracted by thenoyltrifluoroace- tone-trioctylphosphine oxide （TTA-TOPO） in kerosene within 80 min. Extraction efficiency is severely influenced by stoichiometric parameters. Among the stoichiometric parameters, volume ratio of aqueous （A） to extraction （E） solution is the most influential parameter. After extrac- tion, lithium ion could be easily stripped from the extraction solution by acidic solutions. Stripping efficiency decreases with pH of acidic solutions, and the kind of acid does not affect the stripping efficiency. Extraction efficiency main- tains at more than 93 % even when the extraction solution is recycled three times. 65 % of lithium ion can be extracted from seawater by this solvent extraction process when magnesium ion is precipitated by NHaOH prior to solvent extraction process. Other metallic ions in seawater decrease the extraction efficiency of lithium ion.
基金Financial support from the National Natural Science Foundation of China (21276194)the Specialized Research Fund for the Doctoral Program of Chinese Higher Education (20101208110003)the Key Pillar Program of Tianjin Municipal Science and Technology (11ZCKGX02800)
文摘1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fields,especially in
基金the doctorate grant ref.9244/13-1 supplied by CAPES Foundation,Ministry of Education of Brazil
文摘The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. There- fore, this study optimized an innovative process, which does not require a high-temperature calcination step, for lithium extraction from le- pidolite. Mechanical activation and acid digestion were suggested as crucial process parameters, and experimental design and re- sponse-surface methodology were applied to model and optimize the proposed lithium extraction process. The promoting effect of amorphi- zation and the formation of lithium sulfate hydrate on lithium extraction yield were assessed. Several factor combinations led to extraction yields that exceeded 90%, indicating that the proposed process is an effective approach for lithium recovery.
